Crystallization of (20R) 19-Nor-24-Difluoro-1alpha,25-Dihydroxyvitamin D3

ABSTRACT

Disclosed are methods of purifying the compound (20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D 3  to obtain the compound in crystalline form. The methods typically include the steps of dissolving a product containing the compound in a solvent comprising hexane and 2-propanol, cooling the solvent and dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of crystals, and recovering the crystals.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

The present application claims the benefit under 35 U.S.C. §119(e) toU.S. Provisional Patent Application No. 61/652,949, filed on May 30,2012, the content of which is incorporated herein by reference in itsentirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under DK047814 awardedby the National Institutes of Health. The government has certain rightsin the invention.

BACKGROUND

The field of the present invention relates to purification of organiccompounds, and more particularly to the purification of the compound(20R)-19-nor-24-difluoro-1α, 25-dihydroxyvitamin D₃ (referred to hereinas “24F2-DM”) by preparing the compound in crystalline form.

Purification of organic compounds, especially those designated forpharmaceutical use, is of considerable importance for chemistssynthesizing such compounds. Preparation of the compound usuallyrequires many synthetic steps and, therefore, the final product can becontaminated not only with side-products derived from the last syntheticstep of the procedure but also with compounds that were formed inprevious steps. Even chromatographic purification, which is a veryefficient but relatively time-consuming process, does not usuallyprovide compounds which are sufficiently pure to be used as drugs.

Depending on the method used to synthesize 1α-hydroxyvitamin Dcompounds, different minor undesirable compounds can accompany the finalproduct. Thus, for example, if direct C-1 hydroxylation of the 5,6-transgeometric isomer of vitamin D is performed, followed by SeO₂/NMOoxidation and photochemical irradiation, (see Andrews et al., J. Org.Chem. 51, 1635 (1986); Calverley et al., Tetrahedron 43, 4609 (1987);Choudry et al., J. Org. Chem. 58, 1496 (1993)), the final1α-hydroxyvitamin D product can be contaminated with 1β-hydroxy- as wellas 5,6-trans isomers. If the method consists of C-1 allylic oxidation ofthe 4-phenyl-1,2,4-triazoline-3,5-dione adduct of the pre-vitamin Dcompound, followed by cycloreversion of the modified adduct under basicconditions, (see Nevinckx et al., Tetrahedron 47, 9419 (1991); Vanmaeleet al., Tetrahedron 41, 141 (1985) and 40, 1179 (1994); Vanmaele et al.,Tetrahedron Lett. 23. 995 (1982)), one can expect that the desired1α-hydroxyvitamin can be contaminated with the pre-vitamin 5(10),6,8-triene and 1β-hydroxy isomer. One of the most useful C-1hydroxylation methods, of very broad scope and numerous applications, isthe experimentally simple procedure elaborated by Paaren et al., J. Org.Chem. 45, 3253 (1980); and Proc. Natl. Acad. Sci. U.S.A. 75, 2080(1978). This method consists of allylic oxidation of 3,5-cyclovitamin Dderivatives, readily obtained from the buffered solvolysis of vitamin Dtosylates, with SeO₂/t-BuOOH and subsequent acid-catalyzedcycloreversion to the desired 1α-hydroxy compounds. Taking into accountthis synthetic path it is reasonable to assume that the final productcan be contaminated with the 1α-hydroxy epimer, the 5,6-trans isomer andthe pre-vitamin D form. 1α-hydroxyvitamin D₄ is another undesirablecontaminant found in 1α-hydroxyvitamin D compounds synthesized fromvitamin D₂ or from ergosterol. 1α-hydroxyvitamin D₄ results from C-1oxidation of vitamin D₄, which in turn is derived from contamination ofthe commercial ergosterol material. Typically, the final product maycontain up to about 1.5% by weight 1α-hydroxyvitamin D₄. Thus, apurification technique that would eliminate or substantially reduce theamount of 1α-hydroxyvitamin D₄ in the final product to less than about0.1-0.2% would be highly desirable.

The vitamin D conjugated triene system is not only heat- andlight-sensitive but it is also prone to oxidation, leading to thecomplex mixture of very polar compounds. Oxidation usually happens whena vitamin D compound has been stored for a prolonged time. Other typesof processes that can lead to a partial decomposition of vitamin Dcompounds consist of some water-elimination reactions. The driving forcefor these reactions is the allylic (1α-) and homoallylic (3β-) positionof the hydroxy groups. The presence of such above-mentioned oxidationand elimination products can be easily detected by thin-layerchromatography.

Usually, all 1α-hydroxylatation procedures require at least onechromatographic purification. However, even chromatographically purified1α-hydroxyvitamin D compounds, although showing consistent spectroscopicdata that suggests homogeneity, do not meet the purity criteria requiredfor therapeutic agents that can be orally, parenterally or transdermallyadministered. Therefore, it is evident that a suitable method ofpurification of the 1α-hydroxylated vitamin D compound 24F2-DM isrequired.

SUMMARY

Disclosed herein are methods of purifying 24F2-DM by means ofcrystallization to obtain 24F2-DM in crystalline form. The solvent playsan important role in the crystallization process, and is typically anindividual liquid substance or a suitable mixture of different liquids.For crystallizing 24F2-DM, the most appropriate solvent and/or solventsystem is characterized by the following factors:

(1) low toxicity;

(2) low boiling point;

(3) significant dependence of solubility properties with regard totemperature (condition necessary for providing satisfactorycrystallization yield); and

(4) relatively low cost.

Interestingly, hexane, so frequently used for crystallization purposes,was found less suitable as the sole solvent for crystallization of24F2-DM. However, it was found that a mixture of 2-propanol and hexanewas most useful for the crystallization of 24F2-DM. In particular, itwas determined that a mixture of about 10% to about 20% 2-propanol (v/v)with about 90% to about 80% hexane (v/v) (and preferably 15% 2-propanol(v/v) with about 85% hexane (v/v)) performed well. The 2-propanol/hexanesolvent mixture also was easy to remove by evaporation or otherwell-known methods. In all cases, the crystallization process occurredeasily and efficiently. The precipitated crystals were sufficientlylarge to assure their recovery by filtration or other means, and thuswere suitable for x-ray analysis.

Accordingly, the present invention provides a compound having theformula:

in crystalline form. More specifically, the compound may be referred toas (20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃ or “24F2-DM” incrystalline form.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of the three dimensional molecular structurefor 24F2-DM as defined by the atomic positional parameters discoveredand set forth herein.

DETAILED DESCRIPTION

Disclosed herein is the compound(20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D3 (24F2-DM) incrystalline form, a pharmacologically important compound, characterizedby the formula I shown below:

Also disclosed are methods of purifying 24F2-DM. The purificationtechnique involves obtaining the 24F2-DM product in crystalline form byutilizing a crystallization procedure wherein the material to bepurified is dissolved using as the solvent a mixture comprised of2-propanol and hexane to obtain 24F2-DM. Preferably the mixturecomprises from about 10% to about 20% 2-propanol and about 90% to about80% hexane, and preferably about 15% 2-propanol and about 85% hexane (byvolume). Thereafter, the solvent can be removed by evaporation, with orwithout vacuum, or other means as is well known, or the resultantcrystals may be filtered from the mother liquor. The technique can beused to purify a wide range of final products containing 24F2-DMobtained from any known synthesis thereof, and in varyingconcentrations, ranging from microgram amounts to kilogram amounts. Asis well known to those skilled in this art, the amount of solventutilized may be modulated according to the amount of 24F2-DM to bepurified.

EXAMPLES

The following examples are illustrative and should not be interpreted aslimiting the claimed subject matter.

The usefulness and advantages of the present crystallization procedureis shown in the following specific Examples. After crystallization, theprecipitated material was observed under a microscope to confirm itscrystalline form. Yields of crystals were relatively high and theobtained crystals showed a relatively sharp melting point of 182-183° C.(24F2-DM).

The described crystallization process of the synthetic 24F2-DM productrepresents a valuable purification method, which can remove most sideproducts derived from the synthetic path. Such impurity is the result ofthe contamination of starting raw materials. The crystallization processoccurred easily and efficiently. The precipitated crystals weresufficiently large to assure their recovery by filtration, or othermeans, and thus were suitable for x-ray analysis.

Example 1 Crystallization of(20R)-19-nor-24-difluoro-1α25-dihydroxyvitamin D₃ (24F2-DM)

Crystallization from 2-Propanol/Hexane.

(20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃ (24F2-DM) (6 mg), wassuspended in hexane (3 mL) and then 2-propanol was added dropwise to thesuspension. The mixture was heated in a water bath to dissolve thevitamin, then was left at room temperature for about 1 hour, and finallywas kept in a refrigerator for about 48 hours. The precipitated crystalswere filtered off, washed with a small volume of a cold (0° C.)2-propanol/hexane (3:1) mixture and dried to give crystalline material.It should be noted that an excess of 2-propanol should be avoided to getthe point of saturation, (i.e., only about 1 mole or less of 2-propanolshould be added).

Experimental.

A colorless prism-shaped crystal of dimensions 0.56×0.24×0.21 mm wasselected for structural analysis. Intensity data were collected using aBruker AXS Platinum 135 CCD detector controlled with the PROTEUMsoftware suite (Bruker AXS Inc., Madison, Wis.). The x-ray source wasCuKα radiation (1.54178 Å) from a Rigaku RU200 x-ray generator equippedwith Montel optics, operated at 50 kV and 90 mA. The x-ray data wereprocessed with SAINT version 7.06 A (Bruker AXS Inc.) and internallyscaled with SADABS version 2005/1 (Bruker AXS Inc.). The sample wasmounted in a quartz capillary and diffraction data collected at 298 K.The intensity data were measured as a series of phi and omegaoscillation frames each of 1° for 30-60 sec/frame. The detector wasoperated in 1024×1024 mode and was positioned 5.0 cm from the sample.Cell parameters were determined from a non-linear least squares fit of5115 peaks in the range of 3.0<theta<61.5°. The data were merged to forma set of 2949 independent data with R(int)=0.0658.

The monoclinic space group C2 was determined by systematic absences andstatistical tests and verified by subsequent refinement. The structurewas solved by direct methods and refined by full-matrix least-squaresmethods on F², (a) G. M. Sheldrick (1994), SHELXTL Version 5 ReferenceManual, Bruker AXS Inc.; (b) International Tables for Crysuallography,Vol. C, Kluwer: Boston (1995). Hydrogen atom positions were determinedfrom difference peaks and ultimately refined by a riding model withidealized geometry. Non-hydrogen atoms were refined with anisotropicdisplacement parameters. A total of 280 parameters were refined against1 restraint and 2949 data to give wR2=0.1794 and S=1.027 for weights ofw=1/[s²(F²)+(0.1196P)²], where P=[F_(o) ²+2F²]/3. The final R(F) was0.0669 for the 2949 observed data. The largest shift/s.u. was 0.001 inthe final refinement cycle and the final difference map had maxima andminima of 0.228 and −0.200 e/Å₃, respectively. The absolute structurewas determined by refinement of the Flack parameter, H. D. Flack, ActaCryst. A, vol. 39, 876-881 (1983).

The three dimensional structure of 24F2-DM as defined by the followingphysical data and atomic positional parameters described and calculatedherein (Tables 1-8) is illustrated in FIG. 1.

TABLE 1 Crystal data and structure refinement for 24F2-DM.Identification code 2007 feb. 11 Empirical formula C26H42F2O3 Formulaweight  440.60 Temperature 298(2) K Wavelength 1.54178 Å Crystal systemMonoclinic Space group C2 Unit cell dimensions a = 23.882(5) Å α = 90° b= 6.1654(12) Å β = 121.83(3)° c = 19.632(4) Å γ = 90° Volume 2456.0(8)Å³ Z   4 Density (calculated) 1.192 Mg/m³ Absorption coefficient 0.696mm⁻¹ F(000)  960 Crystal size 0.70 × 0.20 × 0.01 mm Theta range for datacollection 2.65 to 62.79° Limiting indices −27 < h < 26, −7 < k < 5, −22< l < 20 Reflections collected 5115 Independent reflections 2949 (R(int)= 0.0658) Completeness to Theta = 62.79 97.4% Max. and min. transmission0.9931 and 0.6415 Refinement method Full-matrix least-squares on F²Data/restraints/parameters 2949/1/280 Goodness-of-fit on F²   1.027Final R indices [I > 2σ(I)] R1 = 0.0669, wR2 = 0.1794 R indices (alldata) R1 = 0.0812, wR2 = 0.1938 Largest diff. peak and hole 0.228 and−0.200 e⁻/Å³

TABLE 2 Atomic coordinates (Å² × 10⁴) and equivalent isotropicdisplacement parameters (Å² × 10³) for 24F2-DM U(eq) is defined as onethird of the trace of the orthogonalized Uij tensor. x y z U(eq) O(1)7791(2)  7357(6) 9362(2) 65(1) O(2) 8325(2) 13611(6) 10408(2)  67(1)C(13) 9071(2) 14375(7) 6662(2) 46(1) F(2) 7592(1) 11566(8) 2797(2) 85(1)C(5) 8998(2) 11683(8) 9616(2) 51(1) F(1) 8124(2)  8914(7) 3583(2) 97(1)C(14) 8581(2) 14018(8) 6948(2) 50(1) C(3) 8802(2) 11904(8) 10755(2) 56(1) C(2) 8472(2)  9722(8) 10504(3)  58(1) O(25) 8404(2) 11739(8)2212(2) 75(1) C(4) 9288(2)  12202(10) 10482(2)  59(1) C(8) 8875(2)14304(8) 7829(2) 50(1) C(10) 8646(3)  9530(8) 9360(3) 60(1) C(11)9669(3) 17024(9) 7815(2) 64(1) C(1) 8146(2)  9375(8) 9611(3) 54(1) C(7)8823(2) 12846(8) 8292(2) 52(1) C(6) 9065(2) 13067(8) 9137(3) 54(1) C(12)9342(2) 16680(8) 6912(2) 57(1) C(18) 9627(2) 12723(8) 7044(2) 54(1)C(15) 8230(2)  11923(10) 6537(3) 61(1) C(17) 8612(2) 13954(8) 5760(2)52(1) C(9) 9199(3) 16504(9) 8103(3) 64(1) C(20) 8910(2) 13579(9) 5242(2)57(1) C(27) 9084(3)  9004(14) 3081(3) 88(2) C(16) 8177(2)  12029(10)5721(2) 64(1) C(23) 8654(2)  12262(10) 3874(3) 68(2) C(24) 8202(2) 10696(10) 3226(3) 63(1) C(25) 8401(2)  9895(10) 2645(3) 63(1) C(22)8382(2)  12996(12) 4384(2) 71(2) C(26) 7907(3)  8192(12) 2071(3) 82(2)C(21) 9300(4)  15514(14) 5254(3) 99(2)

TABLE 3 Bond lengths [Å] for 24F2-DM. O(1)—C(1) 1.439(6) O(1)—H(1A)0.8200 O(2)—C(3) 1.432(6) O(2)—H(2A) 0.8200 C(13)—C(18) 1.521(6)C(13)—C(17) 1.537(6) C(13)—C(12) 1.531(6) C(13)—C(14) 1.558(6)F(2)—C(24) 1.353(6) C(5)—C(6) 1.341(7) C(5)—C(4) 1.493(6) C(5)—C(10)1.508(7) F(1)—C(24) 1.368(7) C(14)—C(8) 1.494(6) C(14)—C(15) 1.519(7)C(14)—H(14A) 0.9800 C(3)—C(2) 1.505(7) C(3)—C(4) 1.524(6) C(3)—H(3A)0.9800 C(2)—C(1) 1.511(6) C(2)—H(2B) 0.9700 O(2)—H(2C) 0.9700O(25)—C(25) 1.422(7) O(25)—H(25A) 0.8200 C(4)—H(4A) 0.9700 C(4)—H(4B)0.9700 C(8)—C(7) 1.330(6) C(8)—C(9) 1.513(7) C(10)—C(1) 1.517(6)C(10)—H(10A) 0.9700 C(10)—H(10B) 0.9700 C(11)—C(9) 1.532(7) C(11)—C(12)1.529(6) C(11)—H(11A) 0.9700 C(11)—H(11B) 0.9700 C(1)—H(1B) 0.9800C(7)—C(6) 1.446(6) C(7)—H(7A) 0.9300 C(6)—H(6A) 0.9300 C(12)—H(12A)0.9700 C(12)—H(12B) 0.9700 C(18)—H(18A) 0.9600 C(18)—H(18B) 0.9600C(18)—H(18C) 0.9600 C(15)—C(16) 1.541(6) C(15)—H(15A) 0.9700C(15)—H(15B) 0.9700 C(17)—C(20) 1.536(6) C(17)—C(16) 1.552(7)C(17)—H(17A) 0.9800 C(9)—H(9A) 0.9700 C(9)—H(9B) 0.9700 C(20)—C(21)1.506(8) C(20)—C(22) 1.522(6) C(20)—H(20A) 0.9800 C(27)—C(25) 1.489(8)C(27)—H(27A) 0.9600 C(27)—H(27B) 0.9600 C(27)—H(27C) 0.9600 C(16)—H(16A)0.9700 C(16)—H(16B) 0.9700 C(23)—C(24) 1.505(7) C(23)—C(22) 1.520(6)C(23)—H(23A) 0.9700 C(23)—H(23B) 0.9700 C(24)—C(25) 1.530(7) C(25)—C(26)1.537(8) C(22)—H(22A) 0.9700 C(22)—H(22B) 0.9700 C(26)—H(26A) 0.9600C(26)—H(26B) 0.9600 C(26)—H(26C) 0.9600 C(21)—H(21A) 0.9600 C(21)—H(21B)0.9600 C(21)—H(21C) 0.9600

TABLE 4 Bond angles [°] for 24F2-DM. C(1)—O(1)—H(1A) 109.5C(3)—O(2)—H(2A) 109.5 C(18)—C(13)—C(17) 111.2(4) C(18)—C(13)—C(12)110.6(4) C(17)—C(13)—C(12) 116.8(4) C(18)—C(13)—C(14) 110.8(3)C(17)—C(13)—C(14) 100.1(3) C(12)—C(13)—C(14) 106.6(3) C(6)—C(5)—C(4)120.5(5) C(6)—C(5)—C(10) 125.2(4) C(4)—C(5)—C(10) 114.3(4)C(8)—C(14)—C(15) 120.4(4) C(8)—C(14)—C(13) 114.5(3) C(15)—C(14)—C(13)103.7(3) C(8)—C(14)—H(14A) 105.7 C(15)—C(14)—H(14A) 105.7C(13)—C(14)—H(14A) 105.7 O(2)—C(3)—C(2) 110.7(3) O(2)—C(3)—C(4) 107.7(4)C(2)—C(3)—C(4) 110.9(4) O(2)—C(3)—H(3A) 109.2 C(2)—C(3)—H(3A) 109.2C(4)—C(3)—H(3A) 109.2 C(1)—C(2)—C(3) 111.5(4) C(1)—C(2)—H(2B) 109.3C(3)—C(2)—H(2B) 109.3 C(1)—C(2)—H(2C) 109.3 C(3)—C(2)—H(2C) 109.3H(2B)—C(2)—H(2C) 108.0 C(25)—O(25)—H(25A) 109.5 C(5)—C(4)—C(3) 113.2(4)C(5)—C(4)—H(4A) 108.9 C(3)—C(4)—H(4A) 108.9 C(5)—C(4)—H(4B) 108.9C(3)—C(4)—H(4B) 108.9 H(4A)—C(4)—H(4B) 107.8 C(7)—C(8)—C(14) 123.7(4)C(7)—C(8)—C(9) 125.2(4) C(14)—C(8)—C(9) 111.0(4) C(5)—C(10)—C(1)110.0(4) C(5)—C(10)—H(10A) 109.7 C(1)—C(10)—H(10A) 109.7C(5)—C(10)—H(10B) 109.7 C(1)—C(10)—H(10B) 109.7 H(10A)—C(10)—H(10B)108.2 C(9)—C(11)—C(12) 111.8(4) C(9)—C(11)—H(11A) 109.3C(12)—C(11)—H(11A) 109.3 C(9)—C(11)—H(11B) 109.2 C(12)—C(11)—H(11B)109.3 H(11A)—C(11)—H(11B) 107.9 O(1)—C(1)—C(2) 111.6(4) O(1)—C(1)—C(10)111.5(4) C(2)—C(1)—C(10) 110.9(4) O(1)—C(1)—H(1B) 107.5 C(2)—C(1)—H(1B)107.5 C(10)—C(1)—H(1B) 107.5 C(8)—C(7)—C(6) 126.6(5) C(8)—C(7)—H(7A)116.7 C(6)—C(7)—H(7A) 116.7 C(5)—C(6)—C(7) 128.4(5) C(5)—C(6)—H(6A)115.8 C(7)—C(6)—H(6A) 115.8 C(11)—C(12)—C(13) 111.8(4)C(11)—C(12)—H(12A) 109.2 C(13)—C(12)—H(12A) 109.2 C(11)—C(12)—H(12B)109.2 C(13)—C(12)—H(12B) 109.2 H(12A)—C(12)—H(12B) 107.9C(13)—C(18)—H(18A) 109.5 C(13)—C(18)—H(18B) 109.5 H(18A)—C(18)—H(18B)109.5 C(13)—C(18)—H(18C) 109.5 H(18A)—C(18)—H(18C) 109.5H(18B)—C(18)—H(18C) 109.5 C(14)—C(15)—C(16) 103.7(4) C(14)—C(15)—H(15A)111.0 C(16)—C(15)—H(15A) 111.0 C(14)—C(15)—H(15B) 111.0C(16)—C(15)—H(15B) 111.0 H(15A)—C(15)—H(15B) 109.0 C(13)—C(17)—C(20)119.4(4) C(13)—C(17)—C(16) 103.8(3) C(20)—C(17)—C(16) 112.6(4)C(13)—C(17)—H(17A) 106.8 C(20)—C(17)—H(17A) 106.8 C(16)—C(17)—H(17A)106.8 C(8)—C(9)—C(11) 113.2(4) C(8)—C(9)—H(9A) 108.9 C(11)—C(9)—H(9B)108.9 C(8)—C(9)—H(9B) 108.9 C(11)—C(9)—H(9B) 108.9 H(9A)—C(9)—H(9B)107.8 C(21)—C(20)—C(22) 110.4(4) C(21)—C(20)—C(17) 111.7(4)C(22)—C(20)—C(17) 111.5(4) C(21)—C(20)—H(20A) 107.7 C(22)—C(20)—H(20A)107.7 C(17)—C(20)—H(20A) 107.7 C(25)—C(27)—H(27A) 109.5C(25)—C(27)—H(27B) 109.5 H(27A)—C(27)—H(27B) 109.5 C(25)—C(27)—H(27C)109.5 H(27A)—C(27)—H(27C) 109.5 H(27B)—C(27)—H(27C) 109.5C(15)—C(16)—C(17) 107.2(4) C(15)—C(16)—H(16A) 110.3 C(17)—C(16)—H(16A)110.3 C(15)—C(16)—H(16B) 110.3 C(17)—C(16)—H(16B) 110.3H(16A)—C(16)—H(16B) 108.5 C(24)—C(23)—C(22) 112.5(4) C(24)—C(23)—H(23A)109.1 C(22)—C(23)—H(23A) 109.1 C(24)—C(23)—H(23B) 109.1C(22)—C(23)—H(23B) 109.1 H(23A)—C(23)—H(23B) 107.8 F(2)—C(24)—F(1)104.1(4) F(2)—C(24)—C(23) 109.2(5) F(1)—C(24)—C(23) 108.2(4)F(2)—C(24)—C(25) 108.7(3) F(1)—C(24)—C(25) 107.6(5) C(23)—C(24)—C(25)118.1(4) O(25)—C(25)—C(27) 106.9(5) O(25)—C(25)—C(24) 106.8(5)C(27)—C(25)—C(24) 111.5(4) O(25)—C(25)—C(26) 110.6(4) C(27)—C(25)—C(26)110.8(5) C(24)—C(25)—C(26) 110.2(4) C(23)—C(22)—C(20) 114.0(4)C(23)—C(22)—H(22A) 108.7 C(20)—C(22)—H(22A) 108.7 C(23)—C(22)—H(22B)108.7 C(20)—C(22)—H(22B) 108.7 H(22A)—C(22)—H(22B) 107.6C(25)—C(26)—H(26A) 109.5 C(25)—C(26)—H(26B) 109.5 H(26A)—C(26)—H(26B)109.5 C(25)—C(26)—H(26C) 109.5 H(26A)—C(26)—H(26C) 109.5H(26B)—C(26)—H(26C) 109.5 C(20)—C(21)—H(21A) 109.5 C(20)—C(21)—H(21B)109.5 H(21A)—C(21)—H(21B) 109.5 C(20)—C(21)—H(21C) 109.5H(21A)—C(21)—H(21C) 109.5 H(21B)—C(21)—H(21C) 109.5

TABLE 5 Anisotropic displacement parameters (Å² × 10³) for 24F2-DM. Theanisotropic displacement factor exponent takes the form: −2π²[h²a*²U₁₁ +. . . + 2hka*b*U₁₂. U11 U22 U33 U23 U13 U12 O(1) 75 (2) 56 (2) 64 (2) 0(2) 37 (2) −12 (2)  O(2) 85 (2) 55 (2) 82 (2) 4 (2) 57 (2)  1 (2) C(13)53 (2) 40 (2) 49 (2) 2 (2) 30 (2)  3 (2) F(2) 60 (2) 125 (3)  63 (1) −17(2)  28 (1)  1 (2) C(5) 55 (2) 52 (3) 58 (2) −1 (2)  37 (2) −4 (2) F(1)127 (3)  100 (3)  91 (2) 3 (2) 75 (2) −28 (2)  C(14) 54 (2) 44 (2) 58(2) 2 (2) 34 (2)  0 (2) C(3) 62 (2) 56 (3) 54 (2) 4 (2) 34 (2) −1 (2)C(2) 63 (2) 54 (3) 58 (2) 11 (2)  38 (2) −1 (2) O(25) 90 (2) 83 (3) 60(2) 6 (2) 45 (2) −5 (2) C(4) 56 (2) 72 (3) 49 (2) 2 (2) 28 (2) −4 (2)C(8) 57 (2) 47 (3) 59 (2) 1 (2) 38 (2)  3 (2) C(10) 80 (3) 54 (3) 62 (2)−1 (2)  48 (2) −1 (3) C(11) 90 (3) 49 (3) 56 (2) −4 (2)  40 (2) −17 (3) C(1) 63 (2) 45 (3) 61 (2) 8 (2) 37 (2)  0 (2) C(7) 62 (2) 50 (3) 58 (2)−2 (2)  42 (2) −3 (2) C(6) 56 (2) 52 (3) 62 (2) −1 (2)  36 (2)  0 (2)C(12) 71 (3) 42 (3) 63 (2) 0 (2) 40 (2) −9 (3) C(18) 55 (2) 53 (3) 52(2) −1 (2)  26 (2)  3 (2) C(15) 63 (2) 66 (3) 67 (2) −6 (3)  42 (2) −12(3)  C(17) 57 (2) 52 (3) 50 (2) 1 (2) 31 (2)  5 (2) C(9) 94 (3) 46 (3)59 (2) −9 (2)  44 (2) −6 (3) C(20) 58 (2) 67 (3) 52 (2) −5 (2)  32 (2)−5 (2) C(27) 81 (3) 109 (6)  76 (3) 6 (4) 43 (3)  8 (4) C(16) 69 (3) 66(3) 59 (2) −3 (3)  35 (2) −6 (3) C(23) 70 (3) 89 (4) 53 (2) −11 (3)  39(2) −10 (3)  C(24) 61 (3) 85 (4) 46 (2) 1 (2) 30 (2) −7 (3) C(25) 64 (3)73 (4) 55 (2) 3 (3) 33 (2) −4 (3) C(22) 66 (3) 98 (4) 49 (2) −8 (3)  31(2) −1 (3) C(26) 95 (4) 80 (4) 75 (3) −13 (3)  48 (3) −19 (3)  C(21) 122(5)  124 (6)  75 (3) −26 (4)  68 (3) −49 (5) 

TABLE 6 Hydrogen coordinates (Å² × 10⁴) and isotropic displacementparameters (Å² × 10³) for 24F2-DM. x y z U(eq) H(1A) 7993 6436 9709 98H(2A) 8012 13327 10455 101 H(14A) 8249 15164 6691 60 H(3A) 9039 1201911341 67 H(2B) 8797 8593 10787 66 H(2C) 8143 9613 10650 66 H(25A) 805511798 1779 113 H(4A) 9440 13693 10577 71 H(4B) 9667 11276 10802 71H(10A) 8964 8360 9604 73 H(10B) 8424 9384 8782 73 H(11A) 10056 161048096 77 H(11B) 9813 18520 7945 77 H(1B) 7826 10546 9341 65 H(7A) 861011555 8049 62 H(6A) 9297 14334 9379 65 H(12A) 9661 16953 6760 68 H(12B)8984 17711 6630 68 H(18A) 9923 12972 6860 82 H(18B) 9447 11287 6895 82H(18C) 9862 12868 7616 82 H(15A) 7797 11855 6468 73 H(15B) 8484 106706843 73 H(17A) 8321 15218 5536 63 H(9A) 9443 16555 8684 77 H(9B) 886017610 7905 77 H(20A) 9214 12348 5470 69 H(27A) 9385 10090 3436 132H(27B) 9202 8588 2702 132 H(27C) 9104 7759 3387 132 H(16A) 7722 122575293 76 H(16B) 8331 10685 5618 76 H(23A) 8721 13521 3629 81 H(23B) 907911576 4216 81 H(22A) 8110 11847 4395 85 H(22B) 8102 14250 4132 123H(26A) 7472 8808 1788 123 H(26B) 7913 6956 2373 123 H(26C) 8025 77511695 123 H(21A) 9629 15868 5799 148 H(21B) 9010 16728 5007 148 H(21C)9511 15179 4964 148

TABLE 7 Torsion angles [deg] for 24F2-DM. C(18)—C(13)—C(14)—C(8) 62.4(5)C(17)—C(13)—C(14)—C(8) 179.8(4) C(12)—C(13)—C(14)—C(8) −58.1(5)C(18)—C(13)—C(14)—C(15) −70.8(4) C(17)—C(13)—C(14)—C(15) 46.7(4)C(12)—C(13)—C(14)—C(15) 168.7(4) O(2)—C(3)—C(2)—C(1) 64.7(5)C(4)—C(3)—C(2)—C(1) −54.8(5) C(6)—C(5)—C(4)—C(3) 130.9(5)C(10)—C(5)—C(4)—C(3) −49.6(6) O(2)—C(3)—C(4)—C(5) −71.4(5)C(2)—C(3)—C(4)—C(5) 49.9(6) C(15)—C(14)—C(8)—C(7) −3.6(7)C(13)—C(14)—C(8)—C(7) −128.4(5) C(15)—C(14)—C(8)—C(9) 179.7(4)C(13)—C(14)—C(8)—C(9) 54.9(5) C(6)—C(5)—C(10)—C(1) −128.4(5)C(4)—C(5)—C(10)—C(1) 52.1(5) C(3)—C(2)—C(1)—O(1) −175.9(4)C(3)—C(2)—C(1)—C(10) 59.1(6) C(5)—C(10)—C(1)—O(1) 178.8(3)C(5)—C(10)—C(1)—C(2) −56.1(5) C(14)—C(8)—C(7)—C(6) −176.5(4)C(9)—C(8)—C(7)—C(6) −0.3(7) C(4)—C(5)—C(6)—C(7) 179.8(4)C(10)—C(5)—C(6)—C(7) 0.3(8) C(8)—C(7)—C(6)—C(5) 176.8(5)C(9)—C(11)—C(12)—C(13) −56.0(6) C(18)—C(13)—C(12)—C(11) −63.4(5)C(17)—C(13)—C(12)—C(11) 168.1(4) C(14)—C(13)—C(12)—C(11) 57.2(5)C(8)—C(14)—C(15)—C(16) −164.9(4) C(13)—C(14)—C(15)—C(16) −35.2(5)C(18)—C(13)—C(17)—C(20) −48.2(6) C(12)—C(13)—C(17)—C(20) 80.1(5)C(14)—C(13)—C(17)—C(20) −165.3(4) C(18)—C(13)—C(17)—C(16) 78.2(4)C(12)—C(13)—C(17)—C(16) −153.6(4) C(14)—C(13)—C(17)—C(16) −39.0(4)C(7)—C(8)—C(9)—C(11) 133.5(5) C(14)—C(8)—C(9)—C(11) −49.9(5)C(12)—C(11)—C(9)—C(8) 51.1(6) C(13)—C(17)—C(20)—C(21) −61.0(6)C(16)—C(17)—C(20)—C(21) 177.0(4) C(13)—C(17)—C(20)—C(22) 175.0(5)C(16)—C(17)—C(20)—C(22) 53.0(6) C(14)—C(15)—C(16)—C(17) 10.4(5)C(13)—C(17)—C(16)—C(15) 18.5(5) C(20)—C(17)—C(16)—C(15) 149.0(4)C(22)—C(23)—C(24)—F(2) 52.8(6) C(22)—C(23)—C(24)—F(1) −60.0(6)C(22)—C(23)—C(24)—C(25) 177.5(5) F(2)—C(24)—C(25)—O(25) 61.0(5)F(1)—C(24)—O(25)—O(25) 173.2(4) C(23)—C(24)—C(25)—O(25) −64.0(5)F(2)—C(24)—C(25)—C(27) 177.4(5) F(1)—C(24)—C(25)—C(27) −70.4(6)C(23)—C(24)—C(25)—C(27) 52.4(7) F(2)—C(24)—C(25)—C(26) −59.1(6)F(1)—C(24)—C(25)—C(26) 53.1(5) C(23)—C(24)—C(25)—C(26) 175.9(5)C(24)—C(23)—C(22)—C(20) 150.8(5) C(21)—C(20)—C(22)—C(23) 64.3(7)C(17)—C(20)—C(22)—C(23) −170.9(5)

TABLE 8 Observed and calculated structure factors for 24F2-DM. h k l10Fc 10Fc 10s 1 −7 0 41 42 4 3 −7 0 38 34 6 0 −6 0 53 41 8 2 −6 0 43 5310 4 −6 0 11 27 10 6 −6 0 63 68 4 10 −6 0 0 31 1 1 −5 0 65 57 6 3 −5 0310 315 8 5 −5 0 131 133 8 7 −5 0 143 185 7 9 −5 0 23 18 23 11 −5 0 3647 8 13 −5 0 91 67 10 15 −5 0 82 62 10 0 −4 0 683 673 48 2 −4 0 87 87 44 −4 0 282 277 6 6 −4 0 31 27 8 8 −4 0 0 13 1 10 −4 0 59 60 8 12 −4 0 8199 10 14 −4 0 14 30 14 16 −4 0 64 55 5 18 −4 0 55 51 16 1 −3 0 313 32315 3 −3 0 73 82 5 7 −3 0 185 179 6 9 −3 0 258 262 7 11 −3 0 211 177 6 13−3 0 88 89 6 15 −3 0 55 68 7 17 −3 0 78 92 5 19 −3 0 71 65 6 21 −3 0 2828 8 0 −2 0 1114 1129 40 2 −2 0 208 206 13 4 −2 0 795 756 34 6 −2 0 512529 28 8 −2 0 210 179 11 10 −2 0 246 231 8 12 −2 0 174 177 6 14 −2 0 8584 5 16 −2 0 87 99 7 18 −2 0 41 48 14 20 −2 0 114 102 8 22 −2 0 31 33 141 −1 0 1222 1167 35 3 −1 0 1786 1655 83 5 −1 0 1028 1026 42 7 −1 0 657823 39 9 −1 0 202 252 11 11 −1 0 128 136 10 13 −1 0 46 36 12 15 −1 0 225216 7 17 −1 0 149 139 5 19 −1 0 41 51 17 21 −1 0 42 40 14 2 0 0 866 87644 4 0 0 2245 2228 115 6 0 0 185 242 10 8 0 0 305 354 16 10 0 0 38 24 2112 0 0 306 301 11 14 0 0 213 215 6 16 0 0 62 62 15 18 0 0 0 5 1 20 0 027 30 26 1 1 0 1218 1167 63 3 1 0 1655 1656 94 5 1 0 989 1026 55 9 1 0210 231 11 11 1 0 138 136 11 13 1 0 35 36 29 15 1 0 219 216 11 17 1 0126 140 10 19 1 0 39 51 32 21 1 0 53 41 16 2 2 0 224 209 11 4 2 0 758755 41 6 2 0 550 532 26 8 2 0 204 180 12 10 2 0 242 328 14 12 2 0 183176 13 14 2 0 91 84 12 16 2 0 89 99 12 18 2 0 44 47 25 −6 2 2 749 742 35−4 2 2 169 161 9 −2 2 2 211 214 9 0 2 2 489 463 25 2 2 2 576 530 25 4 22 467 442 24 6 2 2 234 218 13 8 2 2 170 152 13 10 2 2 142 130 7 12 2 2209 212 13 14 2 2 104 96 10 16 2 2 100 107 10 20 2 2 49 49 15 −21 3 2 1833 18 −19 3 2 178 160 12 −17 3 2 65 59 17 −15 3 2 153 162 10 −13 3 2 101125 12 9 3 2 189 167 11 11 3 2 93 78 11 13 3 2 0 30 1 15 3 2 41 64 35 193 2 43 35 20 16 4 2 41 37 26 −3 −7 3 41 44 4 −1 −7 3 20 15 20 −12 −6 344 44 6 −10 −6 3 34 29 9 −8 −6 3 30 19 11 −6 −6 3 57 59 5 −4 −6 3 84 794 −2 −6 3 80 81 4 0 −6 3 70 69 4 2 −6 3 19 13 18 4 −6 3 25 28 24 6 −6 30 18 1 8 −6 3 0 15 1 −17 −5 3 28 24 10 −15 −5 3 39 35 9 −13 −5 3 50 64 7−11 −5 3 66 72 20 −9 −5 3 87 82 7 −7 −5 3 288 270 8 −5 −5 3 155 129 9 −3−5 3 106 88 7 −1 −5 3 156 154 5 1 −5 3 153 160 6 3 −5 3 162 160 6 5 −5 375 69 10 7 −5 3 78 93 10 9 −5 3 1 48 1 11 −5 3 27 8 27 13 −5 3 22 9 22−20 −4 3 35 23 10 −18 −4 3 0 24 1 −16 −4 3 59 75 13 −14 −4 3 103 134 12−12 −4 3 33 32 14 −10 −4 3 83 82 5 −8 −4 3 140 136 4 −6 −4 3 104 102 3−4 −4 3 470 447 9 −2 −4 3 140 128 3 0 −4 3 329 319 8 2 −4 3 83 78 4 4 −43 209 203 6 6 −4 3 209 203 9 8 −4 3 139 143 9 10 −4 3 111 120 10 12 −4 30 46 1 14 −4 3 28 21 27 16 −4 3 27 40 27 −21 −3 3 53 52 8 −19 −3 3 66 607 −17 −3 3 54 12 16 −15 −3 3 95 92 5 −13 −3 3 51 62 7 −11 −3 3 73 77 6−9 −3 3 3 329 7 −7 −3 3 191 185 11 −5 −3 3 213 213 12 −3 −3 3 169 199 10−1 −3 3 309 290 16 1 −3 3 155 167 11 3 −3 3 258 237 15 5 −3 3 406 389 147 −3 3 264 260 7 −7 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170 144 810 0 13 57 43 7 −25 1 13 83 82 11 −23 1 13 100 89 10 −21 1 13 83 90 11−19 1 13 124 124 9 −17 1 13 242 247 14 −15 1 13 169 189 13 −13 1 13 4139 30 −11 1 13 142 156 14 −9 1 13 291 292 10 −7 1 13 141 129 7 −5 1 13117 115 5 −3 1 13 97 107 7 −1 1 13 171 163 7 1 1 13 129 123 14 3 1 13116 121 8 5 1 13 91 89 11 7 1 13 149 136 8 −14 2 13 66 87 15 −12 2 13286 283 16 −10 2 13 138 141 10 −8 2 13 113 123 9 −6 2 13 242 232 11 −4 213 112 122 6 −2 2 13 195 186 8 0 2 13 104 85 6 2 2 13 48 54 10 4 2 13 4346 11 6 2 13 155 146 13 8 2 13 61 54 6 −9 3 13 75 80 12 −7 3 13 291 27915 −5 3 13 153 159 11 −1 3 13 110 103 6 1 3 13 90 81 6 3 3 13 0 25 1 5 313 87 80 6 7 3 13 43 42 12 −4 4 13 51 41 17 −2 4 13 34 54 33 0 4 13 9585 8 2 4 13 71 70 10 4 4 13 35 3 35 −15 −5 14 150 136 6 −13 −5 14 170139 6 −11 −5 14 143 124 7 −9 −5 14 30 36 29 −7 −5 14 58 64 13 −5 −5 1463 57 11 −1 −5 14 3 24 3 −20 −4 14 36 16 22 −18 −4 14 74 76 6 −16 −4 14156 143 7 −14 −4 14 76 99 11 −12 −4 14 200 198 19 −10 −4 14 23 20 22 −8−4 14 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−9 1 17 159 169 14 −7 1 17 111 130 6 −5 1 17 32 33 24 −3 1 1718 36 17 −1 1 17 65 62 8 1 1 17 33 43 32 −20 2 17 75 93 12 −18 2 17 190186 10 −16 2 17 91 92 12 −14 2 17 103 113 11 −12 2 17 80 89 9 −10 2 17144 155 23 −8 2 17 199 217 16 20 2 0 121 101 9 3 0 194 176 15 13 3 0 8287 13 15 3 0 68 61 17 17 3 0 80 92 14 −3 −7 1 69 70 3 −1 −7 1 13 28 13 1−7 1 55 50 3 −8 −6 1 48 49 5 −6 −6 1 57 66 15 −4 −6 1 24 25 14 −2 −6 157 53 5 0 −6 1 103 101 4 2 −6 1 110 132 6 4 −6 1 205 208 6 8 −6 1 86 928 10 −6 1 84 81 8 −17 −5 1 50 52 14 −15 −5 1 72 47 11 −13 −5 1 43 42 12−11 −5 1 11 31 10 −9 −5 1 90 122 5 −7 −5 1 84 95 6 −5 −5 1 92 112 6 −3−5 1 343 329 10 −1 −5 1 28 31 16 1 −5 1 160 164 6 3 −5 1 96 93 5 5 −5 1163 168 20 7 −5 1 37 30 7 9 −5 1 25 29 25 11 −5 1 10 27 10 13 −5 1 41 4124 15 −5 1 16 28 16 −18 −4 1 50 46 6 −16 −4 1 75 86 14 −14 −4 1 61 67 9−12 −4 1 46 50 15 −10 −4 1 137 129 6 −8 −4 1 50 46 8 −6 −4 1 138 131 4−4 −4 1 137 125 3 −2 −4 1 221 211 4 0 −4 1 210 196 5 2 −4 1 155 132 5 4−4 1 101 91 6 6 −4 1 250 247 7 8 −4 1 150 142 5 10 −4 1 34 51 33 12 −4 1144 163 5 14 −4 1 67 64 5 16 −4 1 66 74 14 18 −4 1 33 19 33 −21 −3 1 3322 12 −19 −3 1 78 81 7 −17 −3 1 59 63 9 −15 −3 1 31 42 27 −13 −3 1 49 3523 −11 −3 1 106 101 4 −9 −3 1 108 108 4 −7 −3 1 499 448 25 −5 −3 1 752678 38 −3 −3 1 301 295 18 −1 −3 1 424 447 16 1 −3 1 457 428 30 3 −3 1394 438 21 7 −3 1 116 98 6 9 −3 1 271 270 7 11 −3 1 72 54 5 13 −3 1 112129 18 15 −3 1 150 157 22 17 −3 1 70 71 15 19 −3 1 47 56 7 −22 −2 1 5071 7 −20 −2 1 127 106 7 −18 −2 1 36 43 18 −16 −2 1 141 132 6 −14 −2 1 7783 8 −12 −2 1 134 135 5 −10 −2 1 263 250 12 −8 −2 1 258 209 13 −6 −2 1351 372 19 −4 −2 1 287 302 12 −2 −2 1 361 353 19 0 −2 1 225 229 8 2 −2 1366 330 19 8 −2 1 343 330 18 9 −3 3 163 160 6 11 −3 3 250 287 8 13 −3 3218 244 9 15 −3 3 89 93 5 17 −3 3 42 43 8 −22 −2 3 72 74 8 −20 −2 3 6342 10 −18 −2 3 147 148 7 −16 −2 3 76 74 7 −14 −2 3 177 174 5 −12 −2 3186 176 6 −10 −2 3 222 187 12 −8 −2 3 696 768 36 −6 −2 3 160 167 9 −4 −23 368 415 21 −2 −2 3 32 31 9 0 −2 3 406 375 21 2 −2 3 497 479 26 8 −2 3333 350 14 10 −2 3 142 150 6 12 −2 3 131 124 7 14 −2 3 155 168 8 16 −2 3164 189 8 18 −2 3 92 98 6 20 −2 3 45 43 7 −21 −1 3 70 74 17 −19 −1 3 221209 7 −17 −1 3 81 81 7 −15 −1 3 157 160 6 −13 −1 3 474 478 18 −11 −1 3218 255 14 −9 −1 3 304 304 16 −7 −1 3 151 177 9 −5 −1 3 458 481 25 −3 −13 636 628 30 −1 −1 3 1352 1275 47 1 −1 3 453 427 23 3 −1 3 360 364 18 5−1 3 146 137 6 7 −1 3 188 192 11 9 −1 3 85 72 10 11 −1 3 217 221 7 13 −13 256 254 18 15 −1 3 35 23 24 17 −1 3 127 118 8 19 −1 3 36 36 17 −24 0 354 55 11 −22 0 3 277 230 14 −20 0 3 85 92 10 −18 0 3 154 172 10 −16 0 324 31 24 −14 0 3 158 162 7 −12 0 3 267 218 15 −10 0 3 161 161 11 −8 0 31323 1304 68 −6 0 3 715 675 37 −4 0 3 1082 1021 39 −2 0 3 413 433 15 0 03 1456 1433 86 2 0 3 685 671 35 4 0 3 393 493 20 6 0 3 67 68 8 8 0 3 91101 9 10 0 3 72 70 7 12 0 3 230 232 6 14 0 3 208 204 7 16 0 3 58 45 1218 0 3 54 60 12 20 0 3 39 60 15 −23 1 3 149 126 11 −21 1 3 61 75 13 −191 3 194 210 13 −17 1 3 80 60 11 −15 1 3 161 159 7 −13 1 3 463 478 25 −111 3 257 257 12 −9 1 3 312 301 16 −5 1 3 482 482 17 −3 1 3 607 628 22 −11 3 1313 1274 70 1 1 3 454 425 23 3 1 3 365 365 19 5 1 3 132 139 10 7 13 196 192 11 9 1 3 82 72 13 11 1 3 219 227 8 13 1 3 249 254 11 −5 1 5131 141 6 −3 1 5 185 183 10 −1 1 5 945 915 50 3 1 5 646 629 33 5 1 5 147153 10 7 1 5 383 390 16 9 1 5 202 199 8 11 1 5 125 121 7 17 1 5 50 71 6−24 2 5 47 50 21 −22 2 5 69 61 15 −20 2 5 126 133 12 −18 2 5 356 342 18−16 2 5 262 263 14 −14 2 5 348 398 20 −4 2 5 489 472 23 −2 2 5 432 41923 0 2 5 297 275 16 2 2 5 492 480 27 4 2 5 386 364 20 6 2 5 192 199 8 82 5 27 31 26 16 2 5 93 90 10 18 2 5 87 79 8 −23 3 5 9 51 9 −21 3 5 45 6428 −19 3 5 211 190 11 5 3 5 197 194 12 11 3 5 86 91 12 13 3 5 37 27 3615 3 5 48 36 20 17 3 5 19 19 19 8 4 5 83 81 11 10 4 5 43 46 28 12 4 5 2942 29 14 4 5 23 23 23 −14 −6 6 46 62 8 −12 −6 6 68 64 5 −10 −6 6 40 41 9−8 −6 6 17 12 17 −6 −6 6 121 118 5 −4 −6 6 106 102 4 0 −6 6 35 41 20 2−6 6 71 72 9 4 −6 6 33 28 26 6 −6 6 34 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−15 1 8 229 236 12−9 1 8 1168 1081 59 −7 1 8 219 215 12 −5 1 8 151 158 10 −3 1 8 659 65831 −1 1 8 669 598 33 1 1 8 210 204 11 3 1 8 182 199 7 5 1 8 108 97 6 7 18 224 237 10 9 1 8 143 141 11 11 1 8 165 164 20 13 1 8 107 86 10 −15 −511 22 23 22 −13 −5 11 60 45 16 −11 −5 11 46 33 10 −9 −5 11 5 8 5 −7 −511 197 202 7 −5 −5 11 81 85 9 −3 −5 11 136 152 9 −1 −5 11 85 77 9 1 −511 15 30 14 3 −5 11 65 49 10 −22 −4 11 35 37 29 −20 −4 11 41 34 40 −18−4 11 0 12 1 −16 −4 11 100 97 4 −14 −4 11 83 83 5 −12 −4 11 35 91 17 −10−4 11 109 110 10 −8 −4 11 161 189 10 −6 −4 11 108 123 5 −4 −4 11 252 2498 −2 −4 11 129 121 9 0 −4 11 197 191 12 2 −4 11 67 58 12 4 −4 11 94 10210 6 −4 11 18 33 17 −23 −3 11 18 8 18 −21 −3 11 11 15 10 −19 −3 11 81 816 −17 −3 11 124 150 6 −15 −3 11 60 64 7 −13 −3 11 186 172 5 −11 −3 11 7458 7 −9 −3 11 83 75 9 −7 −3 11 182 160 9 −5 −3 11 290 281 9 −3 −3 11 251235 8 −1 −3 11 236 226 8 1 −3 11 126 112 9 3 −3 11 0 40 1 −26 −2 11 4347 20 −24 −2 11 99 87 7 −22 −2 11 43 59 10 −20 −2 11 39 56 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−9 −314 181 174 24 −7 −3 14 109 109 10 −5 −3 14 256 251 14 −3 −3 14 212 224 7−26 −2 14 46 19 16 −24 −2 14 61 53 7 −22 −2 14 22 35 21 −20 −2 14 116134 5 −18 −2 14 161 162 7 −16 −2 14 110 119 7 −14 −2 14 273 260 7 −12 −214 244 229 6 −10 −2 14 92 82 4 −8 −2 14 338 342 9 −6 −2 14 204 194 9 −4−2 14 337 382 16 −2 −2 14 130 141 6 0 −2 14 119 127 7 2 −2 14 41 51 9 4−2 14 77 71 6 −27 −1 14 37 25 22 −25 −1 14 68 62 8 −23 −1 14 35 57 17−21 −1 14 48 60 10 −19 −1 14 96 93 6 −17 −1 14 84 95 6 −15 −1 14 130 1275 −13 −1 14 159 150 5 −11 −1 14 115 112 4 −9 −1 14 229 217 6 −7 −1 14114 115 4 −5 −1 14 188 188 6 −3 −1 14 34 21 11 −1 −1 14 45 42 11 1 −1 1423 34 22 3 −1 14 30 36 17 5 −1 14 65 80 7 7 −1 14 68 58 7 9 −1 14 48 376 −26 −1 14 40 39 15 −24 −1 14 90 83 10 −22 0 14 63 49 10 −20 0 14 27 3427 −18 0 14 70 84 7 −16 0 14 0 4 1 −14 0 14 97 35 7 −12 0 14 360 349 14−10 0 14 87 94 6 −8 0 14 301 284 10 −6 0 14 233 228 6 −4 0 14 218 201 6−2 0 14 219 215 6 0 0 14 141 130 5 2 0 14 91 72 5 4 0 14 53 54 10 6 0 140 8 1 8 0 14 0 3 1 −25 1 14 63 62 12 −23 1 14 59 57 15 −21 1 14 65 60 13−19 1 14 95 94 10 −17 1 14 88 96 11 −15 1 14 126 128 9 −13 1 14 141 1497 −11 1 14 110 111 6 −9 1 14 227 218 9 −7 1 14 113 115 6 −5 1 14 183 1906 −3 1 14 25 19 24 −1 1 14 41 42 23 1 1 14 28 33 27 3 1 14 34 37 34 5 114 76 80 6 −16 2 14 106 118 10 −14 2 14 264 260 11 −12 2 14 238 229 11−6 2 17 83 101 7 −4 2 17 72 86 7 −2 2 17 14 30 14 0 2 17 42 25 11 2 2 1715 32 14 −15 3 17 67 83 15 −13 3 17 97 78 10 −11 3 17 92 91 11 −9 3 17103 97 9 −7 3 17 50 62 20 −5 3 17 103 101 6 −3 3 17 142 124 7 −1 3 17 4636 9 −10 4 17 18 48 17 −8 4 17 20 52 20 −6 4 17 50 51 14 −4 4 17 36 4219 −16 −4 18 31 23 14 −14 −4 18 43 45 8 −12 −4 18 82 80 5 −10 −4 18 7550 9 −8 −4 18 0 30 1 −21 −3 18 20 22 20 −19 −3 18 50 49 19 −17 −3 18 2947 23 −15 −3 18 135 123 6 −13 −3 18 19 27 16 −11 −3 18 154 137 8 −9 −318 88 78 9 −7 −3 18 89 86 6 −24 −2 18 0 8 1 −22 −2 18 131 107 8 −20 −218 43 42 10 −18 −2 18 22 23 22 −16 −2 18 54 44 6 −14 −2 18 78 104 12 −12−2 18 64 68 10 −10 −2 18 102 96 7 −8 −2 18 42 45 12 −6 −2 18 121 136 7−4 −2 18 40 43 12 −2 −2 18 79 76 6 −25 −1 18 56 62 7 −23 −1 18 138 113 7−21 −1 18 111 108 5 −19 −1 18 0 17 1 −17 −1 18 128 125 19 −15 −1 18 119134 9 −13 −1 18 187 204 10 −11 −1 18 174 160 10 −9 −1 18 109 88 5 −7 −118 150 139 8 −5 −1 18 78 67 7 −3 −1 18 40 37 14 −1 0 18 69 61 8 1 0 1836 31 13 −24 0 18 81 79 6 −20 0 18 56 51 10 −18 0 18 48 51 11 −16 0 1871 86 11 −14 0 18 81 100 8 −12 0 18 123 135 6 −10 0 18 186 221 11 −8 018 182 223 11 −6 0 18 153 140 5 −4 0 18 55 61 7 −2 0 18 44 17 12 0 0 1844 41 11 10 −2 1 444 448 14 12 −2 1 213 219 6 14 −2 1 66 68 9 16 −2 1111 111 7 18 −2 1 26 51 25 20 −2 1 24 13 24 −23 −1 1 42 29 12 −21 −1 176 65 8 −19 −1 1 58 59 8 −17 −1 1 66 68 8 −15 −1 1 66 74 6 −13 −1 1 9395 5 −11 −1 1 727 708 37 −9 −1 1 342 398 18 −7 −1 1 436 450 16 −5 −1 11157 1181 41 −3 −1 1 1214 1185 47 −1 −1 1 773 738 21 3 −1 1 556 514 19 5−1 1 602 581 30 7 −1 1 149 182 9 9 −1 1 197 196 11 11 −1 1 289 283 9 13−1 1 143 142 6 15 −1 1 98 97 6 17 −1 1 78 88 9 19 −1 1 117 92 7 21 −1 144 47 12 −22 0 1 70 67 10 −20 0 1 75 56 11 −18 0 1 0 50 1 −16 0 1 65 7411 −14 0 1 68 53 9 −12 0 1 52 67 21 −10 0 1 460 501 24 −8 0 1 114 127 9−6 0 1 486 469 25 −4 0 1 1594 1546 32 −2 0 1 314 326 16 0 0 1 229 229 82 0 1 495 493 25 4 0 1 1308 1448 67 6 0 1 94 111 7 8 0 1 218 255 12 10 01 132 149 9 12 0 1 203 207 8 14 0 1 200 204 6 16 0 1 128 121 6 18 0 1 9991 10 −21 1 1 77 46 12 −19 1 1 65 58 13 −17 1 1 53 68 19 −15 1 1 80 7310 −13 1 1 106 94 12 −11 1 1 726 709 37 −7 1 1 457 447 22 −5 1 1 11421182 59 −3 1 1 1172 1188 43 −1 1 1 736 735 28 1 1 1 2044 1952 105 3 1 1540 517 29 5 1 1 582 584 31 7 1 1 166 182 9 9 1 1 209 197 11 11 1 1 293283 10 13 1 1 160 141 7 15 1 1 87 96 11 17 1 1 78 88 11 19 1 1 92 91 11−22 2 1 99 77 9 −20 2 1 98 106 11 −18 2 1 40 43 37 −16 2 1 141 131 10−14 2 1 90 82 11 −12 2 1 131 136 9 −10 2 1 237 250 15 −8 2 1 236 209 14−6 2 1 378 371 18 −4 2 1 305 301 14 −2 2 1 365 353 18 0 2 1 240 231 12 22 1 371 331 19 4 2 1 258 257 14 6 2 1 1148 1115 59 8 2 1 351 830 18 10 21 444 449 15 12 2 1 213 220 10 15 1 3 0 23 1 19 1 3 56 36 12 −24 2 3 3150 31 −22 2 3 91 74 11 −20 2 3 61 43 16 −18 2 3 153 148 10 −16 2 3 79 7415 −14 2 3 171 176 12 −4 2 3 408 415 19 −2 2 3 33 33 23 0 2 3 400 377 212 2 3 500 477 26 4 2 3 961 390 49 6 2 3 530 505 27 8 2 3 333 531 12 10 23 156 150 8 12 2 3 129 125 15 14 2 3 154 167 10 20 2 3 56 43 10 −21 3 363 52 15 −19 3 3 35 61 34 −17 3 3 0 12 1 −15 3 3 76 92 15 7 3 3 252 25014 9 3 3 168 160 12 11 3 3 243 236 14 17 3 3 53 43 17 19 3 3 0 11 1 10 43 123 120 9 12 4 3 41 46 92 14 4 3 0 20 1 16 4 3 29 40 29 −14 −6 4 20 2117 −12 −6 4 55 58 7 −10 −6 4 56 46 5 −8 −6 4 35 38 10 −6 −6 4 96 95 4 −4−6 4 37 30 7 −2 −6 4 54 51 4 0 −6 4 59 53 4 2 −6 4 157 144 9 4 −6 4 4752 13 6 −6 4 33 32 27 8 −6 4 44 49 13 −17 −5 4 35 42 9 −15 −5 4 39 54 17−13 −5 4 51 57 8 −11 −5 4 120 256 8 −9 −5 4 125 212 7 −7 −5 4 44 37 9 −5−5 4 55 52 7 −3 −5 4 204 189 14 −1 −5 4 137 127 4 1 −5 4 83 75 4 3 −5 489 99 9 5 −5 4 30 38 29 7 −5 4 45 50 16 9 −5 4 34 28 33 11 −5 4 20 17 2013 −5 4 17 11 17 −20 −4 4 58 51 12 −18 −4 4 51 54 8 −16 −4 4 58 58 7 −14−4 4 98 104 6 −12 −4 4 38 49 11 −10 −4 4 163 158 5 −8 −4 4 232 225 5 −6−4 4 187 192 4 −4 −4 4 146 129 4 −2 −4 4 150 144 4 0 −4 4 80 77 4 2 −4 485 73 8 4 −4 4 158 143 7 6 −4 4 0 16 1 8 −4 4 73 59 12 10 −4 4 78 95 1212 −4 4 37 31 37 14 −4 4 25 14 25 −23 −3 4 40 34 10 −21 −3 4 66 59 6 −19−3 4 36 22 15 −17 −3 4 169 269 10 −15 −3 4 233 223 7 −13 −3 4 333 349 8−11 −3 4 102 112 4 −9 −3 4 167 169 4 −7 −3 4 181 169 11 −9 −3 6 93 91 3−7 −3 6 292 283 8 −5 −3 6 308 270 16 −3 −3 6 86 54 12 −1 −3 6 144 134 71 −3 6 52 65 12 3 −3 6 147 226 7 5 −3 6 260 271 13 7 −3 6 192 179 11 9−3 6 115 114 10 −24 −2 6 38 18 16 −22 −2 6 58 60 9 −20 −2 6 108 208 5−18 −2 6 84 84 5 −16 −2 6 61 61 6 −14 −2 6 310 324 6 −12 −2 6 234 244 7−10 −2 6 52 38 19 −8 −2 6 243 225 13 −6 −2 6 304 520 16 −4 −2 6 502 50227 −2 −2 6 433 368 22 0 −2 6 301 267 17 2 −2 6 287 258 16 6 −2 6 94 81 58 −2 6 112 119 7 10 −2 6 165 166 8 12 −2 6 28 23 16 14 −2 6 50 52 7 16−2 6 15 35 15 −23 −1 6 119 117 8 −21 −1 6 87 65 10 −19 −1 6 99 93 7 −17−1 6 121 121 6 −15 −1 6 235 239 7 −13 −1 6 90 88 14 −11 −1 6 245 219 13−9 −1 6 0 13 1 −7 −1 6 353 345 16 −5 −1 6 645 606 23 −3 −1 6 493 472 18−1 −1 6 581 572 19 1 −1 6 488 464 17 3 −1 6 483 519 25 5 −1 6 157 158 107 −1 6 149 159 5 9 −1 6 191 184 6 11 −1 6 112 106 7 13 −1 6 151 149 8 15−1 6 45 44 12 17 −1 6 40 17 11 −26 0 6 11 17 10 −24 0 6 0 3 1 −22 0 6 6166 13 −20 0 6 92 110 10 −18 0 6 55 34 15 −16 0 6 42 67 24 −14 0 6 17 1916 −12 0 6 573 520 30 −10 0 6 1062 977 54 −8 0 6 1553 1406 80 −6 0 6 592550 21 −4 0 6 276 283 10 −2 0 6 85 103 5 0 0 6 205 181 8 2 0 6 615 73131 4 0 6 99 105 9 6 0 6 184 162 11 8 0 6 86 86 6 10 0 6 88 91 10 12 0 6102 99 5 14 0 6 160 149 6 16 0 6 134 119 9 18 0 6 25 16 25 −25 1 6 0 131 −23 1 6 100 116 10 −21 1 6 92 85 11 −19 1 6 102 93 12 −17 1 6 123 11910 −15 1 6 249 138 12 −13 1 6 88 89 14 −11 1 6 236 220 14 −9 1 6 24 1124 −7 1 6 344 345 13 −5 1 6 655 606 33 −3 1 6 523 473 25 −1 1 6 513 57231 15 1 8 43 43 12 −24 2 8 99 100 11 −22 2 8 99 114 15 −20 2 8 370 32717 −18 2 8 395 372 19 −6 2 8 302 282 17 −4 2 8 166 145 12 −2 2 8 215 19713 0 2 8 253 238 15 2 2 8 238 235 9 4 2 8 216 231 7 6 2 8 308 308 9 8 28 173 272 7 10 2 8 52 60 10 12 2 8 84 91 7 14 2 8 17 7 17 −23 3 8 34 1933 −1 3 8 275 269 15 1 3 8 135 131 9 3 3 8 223 224 12 5 3 8 159 161 12 73 8 32 17 31 9 3 8 45 50 14 11 3 8 152 147 8 13 3 8 0 19 1 4 4 8 159 16211 6 4 8 109 108 9 8 4 8 51 38 17 10 4 8 75 45 20 12 4 8 45 18 25 −12 −69 0 25 1 −10 −6 9 78 92 7 −8 −6 9 56 55 6 −4 −6 9 92 91 7 −2 −6 9 30 2329 0 −6 9 35 32 19 2 −6 9 26 33 25 −19 −5 9 18 19 18 −17 −5 9 0 15 1 −15−5 9 0 25 1 −13 −5 9 23 41 22 −11 −5 9 137 132 5 −9 −5 9 138 142 6 −7 −59 60 64 13 −5 −5 9 114 125 5 −3 −5 9 200 232 11 −1 −5 9 49 45 13 1 −5 962 80 10 3 −5 9 70 57 10 5 −5 9 78 72 9 7 −5 9 30 29 30 −22 −4 9 38 3115 −20 −4 9 29 42 21 −18 −4 9 64 68 7 −16 −4 9 220 206 7 −14 −4 9 204197 5 −12 −4 9 165 167 6 −10 −4 9 108 94 6 −8 −4 9 73 65 7 −6 −4 9 79 746 −4 −4 9 0 16 1 −2 −4 9 93 76 10 0 −4 9 92 95 10 2 −4 9 133 141 9 4 −49 93 96 10 6 −4 9 0 21 1 8 −4 9 64 72 13 10 −4 9 60 55 12 −23 −3 9 46 4014 −21 −3 9 61 63 7 −19 −3 9 112 119 10 −17 −3 9 88 79 6 −15 −3 9 92 9610 −13 −3 9 58 87 8 −11 −3 9 44 48 8 −9 −3 9 165 158 5 −7 −3 9 225 222 6−5 −3 9 234 234 7 −3 −3 9 116 114 5 −1 −3 9 377 362 11 1 −3 9 303 293 153 −3 9 378 364 18 5 −3 9 191 206 13 −24 −2 9 46 50 19 −22 −2 9 41 30 17−20 −2 9 234 226 7 −18 −2 9 132 124 5 −10 0 11 36 46 36 −8 0 11 402 40621 −6 0 11 227 226 13 −4 0 11 656 677 34 −2 0 11 66 80 5 0 0 11 332 3317 2 0 11 116 119 4 4 0 11 42 43 8 6 0 11 113 108 5 8 0 11 8 11 8 10 0 1131 27 21 12 0 11 48 27 9 −27 1 11 0 9 1 −25 1 11 38 56 37 −23 1 11 2 482 −21 1 11 101 100 11 −19 1 11 64 64 15 −17 1 11 203 218 8 −15 1 11 4048 25 −13 1 11 256 260 14 −11 1 11 83 90 8 −9 1 11 414 386 20 −7 1 11329 312 17 −5 1 11 102 89 6 −3 1 11 131 140 6 −1 1 11 95 92 6 1 1 11 3141 18 3 1 11 107 106 6 5 1 11 76 77 7 7 1 11 0 13 1 9 1 11 78 72 6 11 111 125 107 7 −24 2 11 109 87 9 −22 2 11 65 58 14 −12 2 11 38 52 29 −10 211 160 172 12 −8 2 11 228 246 13 −6 2 11 133 130 7 −4 2 11 272 288 8 −22 11 170 174 7 0 2 11 86 74 11 2 2 11 94 96 10 4 2 11 288 298 15 6 2 1144 24 11 8 2 11 131 131 12 10 2 11 30 25 22 12 2 11 29 13 28 −7 3 11 166160 12 −5 3 11 264 280 15 −3 3 11 245 235 13 −1 3 11 248 227 12 1 3 11144 113 10 3 3 11 39 40 17 5 3 11 137 147 16 7 3 11 108 91 12 9 3 11 7255 9 −2 4 11 135 122 9 0 4 11 209 190 11 2 4 11 65 58 12 4 4 11 113 1028 6 4 11 44 32 16 8 4 11 63 47 7 −17 −5 12 26 39 26 −15 −5 12 65 39 11−13 −5 12 43 48 11 −11 −5 12 113 99 8 −9 −5 12 74 70 7 −7 −5 12 122 1165 −5 −5 12 56 58 12 −3 −5 12 91 79 9 −1 −5 12 89 81 9 1 −5 12 54 45 11 3−5 12 42 49 14 −20 −4 12 0 17 1 −18 −4 12 154 134 9 −16 −4 12 48 43 9−14 −4 12 202 200 13 −12 −4 12 115 144 9 −10 −4 12 122 136 13 −8 −4 1233 43 15 −6 −4 12 23 36 22 −4 −4 12 54 66 16 −2 −4 12 49 58 17 0 −4 1293 88 10 2 −4 12 82 84 10 4 −4 12 50 48 14 −23 −3 12 28 30 21 −10 2 1498 82 9 −8 2 14 341 341 11 −6 2 14 206 194 8 −4 2 14 366 382 12 −2 2 14101 141 8 0 2 14 122 128 6 2 2 14 44 51 10 4 2 14 73 71 8 6 2 14 0 14 1−11 3 14 279 267 14 −9 3 14 198 174 11 −7 3 14 105 109 9 −5 3 14 266 25113 −3 3 14 233 223 8 −1 3 14 40 49 15 1 3 14 71 66 15 3 3 14 47 37 11 53 14 0 25 1 −6 4 14 92 104 10 −4 4 14 82 88 10 −2 4 14 115 117 9 0 4 1474 67 9 2 4 14 36 32 14 −15 −5 15 105 94 7 −13 −5 15 66 62 5 −11 −5 15173 149 6 −9 −5 15 5 13 5 −7 −5 15 25 35 24 −5 −5 15 54 52 11 −20 −4 1536 36 20 −18 −4 15 0 22 1 −16 −4 15 68 48 7 −14 −4 15 108 100 8 −12 −415 0 10 1 −10 −4 15 114 114 6 −8 −4 15 151 143 10 −6 −4 15 95 92 10 −4−4 15 65 42 12 −2 −4 15 0 5 1 0 −4 15 46 48 15 −23 −3 15 41 29 10 −21 −315 108 99 5 −19 −3 15 69 83 6 −17 −3 15 189 182 10 −15 −3 15 274 264 8−13 −3 15 168 155 7 −11 −3 15 299 273 10 −9 −3 15 119 115 14 −7 −3 15135 128 23 −5 −3 15 66 78 6 −3 −3 15 32 28 15 −24 −2 15 102 96 6 −22 −215 15 12 14 −20 −2 15 198 215 6 −18 −2 15 58 56 8 −16 −2 15 184 181 11−14 −2 15 211 190 6 −12 −2 15 137 133 4 −10 −2 15 114 122 4 −8 −2 15 130126 8 −6 −2 15 252 272 11 −4 −2 15 177 194 9 −2 −2 15 173 188 8 0 −2 15117 127 6 2 −2 15 57 61 7 4 −2 15 54 39 6 −25 −1 15 44 33 11 −23 −1 1546 48 11 −21 −1 15 104 210 5 −19 −1 15 12 17 12 −17 −1 15 142 149 11 −15−1 15 152 158 11 −13 −1 15 143 128 15 −11 −1 15 384 355 10 −9 −1 15 267242 7 −7 −1 15 338 316 9 −5 −1 15 130 120 6 −3 −1 15 208 197 9 −1 −1 1560 57 8 1 −1 15 164 164 9 3 −1 15 45 51 9 5 −1 15 45 37 10 7 −1 15 64 476 −26 0 15 111 88 6 −24 0 15 104 93 7 −22 0 15 66 66 10 −20 0 15 46 5311 2 0 18 78 81 6 −21 1 18 102 108 20 −19 1 18 6 17 5 −17 1 18 101 125 7−15 1 18 134 135 16 −13 1 18 173 204 8 −11 1 18 151 160 8 −9 1 18 82 878 −7 1 18 132 139 11 −5 1 18 58 67 12 −3 1 18 47 36 11 −1 1 18 68 61 10−20 2 18 40 42 29 −18 2 18 0 23 1 −16 2 18 34 45 99 −14 2 18 97 104 7−12 2 18 66 67 25 −10 2 18 87 96 7 −8 2 18 39 46 16 −6 2 18 131 136 15−4 2 18 46 43 13 −2 2 18 81 76 6 0 2 18 61 50 6 −17 3 18 44 46 22 −15 318 119 122 10 −13 3 18 15 27 15 −11 3 18 158 138 10 −9 3 18 79 78 8 −7 318 81 86 7 −5 3 18 21 27 21 −3 4 18 47 44 9 −12 4 18 79 79 10 −10 4 1840 50 24 −8 4 18 32 31 32 −19 −3 19 29 37 28 −17 −3 19 85 83 5 −15 −3 1932 44 17 −13 −3 19 16 24 16 −11 −3 19 28 27 27 −9 −3 19 125 105 6 −7 −219 64 66 5 −22 −2 19 24 37 24 −20 −2 19 41 49 10 −18 −2 19 77 64 11 −16−2 19 44 48 27 −14 −2 19 56 43 11 −12 −2 19 37 20 19 −10 −2 19 60 63 9−8 −2 19 57 61 9 −6 −2 19 48 52 10 −4 −2 19 92 76 6 −2 −2 19 62 64 5 −23−1 19 132 114 5 −21 −1 19 51 38 8 −19 −1 19 138 123 7 −17 −1 19 105 10415 −15 −1 19 0 27 1 −13 −1 19 62 58 6 −11 −1 19 56 68 7 −9 −1 19 133 1178 −7 −1 19 15 24 15 −5 −1 19 71 57 8 −3 −1 19 42 34 12 −1 −1 19 114 1016 −24 0 19 124 100 14 −22 0 19 186 164 11 −20 0 19 55 62 10 −18 0 19 6463 8 14 2 1 62 68 14 16 2 1 104 110 11 18 2 1 41 51 26 −19 3 1 100 61 19−17 3 1 54 63 21 −15 3 1 0 41 1 −13 3 1 0 34 1 9 3 1 255 271 14 11 3 150 54 22 13 3 1 134 128 9 15 3 1 161 157 10 17 3 1 64 71 17 4 1 60 19 12−3 −7 2 61 59 3 −1 −7 2 80 75 3 1 −7 2 85 86 5 −10 −6 2 73 74 5 −8 −6 249 54 6 −6 −6 2 63 56 10 −4 −6 2 14 8 14 −2 −6 2 90 100 10 0 −6 2 56 6412 2 −6 2 128 133 5 4 −6 2 174 172 8 6 −6 2 140 131 9 8 −6 2 55 63 11 10−6 2 0 39 1 −17 −5 2 10 12 10 −15 −5 2 11 12 11 −13 −5 2 117 115 18 −11−5 2 70 82 13 −9 −5 2 51 52 10 −7 −5 2 96 114 6 −5 −5 2 96 107 4 −3 −5 2188 158 9 −1 −5 2 301 293 11 1 −5 2 416 410 10 3 −5 2 174 167 4 5 −5 2252 248 6 7 −5 2 32 15 32 9 −5 2 63 74 11 11 −5 2 0 19 1 13 −5 2 0 21 115 −5 2 56 47 11 −20 −4 2 40 22 9 −18 −4 2 63 65 6 −16 −4 2 104 119 5−14 −4 2 119 149 7 −12 −4 2 156 178 7 −10 −4 2 254 249 8 −8 −4 2 54 61 6−6 −4 2 373 359 7 −4 −4 2 51 47 7 −2 −4 2 281 271 6 0 −4 2 151 135 5 2−4 2 183 173 4 4 −4 2 153 142 5 6 −4 2 12 7 11 8 −4 2 59 60 5 10 −4 2149 160 5 12 −4 2 174 162 7 14 −4 2 128 119 10 16 −4 2 32 37 32 −21 −3 222 33 21 −19 −3 2 175 161 7 −17 −3 2 59 60 13 −15 −3 2 139 161 9 −13 −32 129 125 5 −11 −3 2 128 109 5 −9 −3 2 123 119 4 −7 −3 2 194 164 11 −5−3 2 581 537 30 −3 −3 2 394 441 20 −1 −3 2 435 392 22 1 −3 2 279 288 153 −3 2 797 694 41 5 −3 2 328 309 18 7 −3 2 150 141 6 9 −3 2 173 166 7 11−3 2 76 78 6 13 −3 2 22 31 22 15 −3 2 61 65 14 17 −3 2 35 25 12 19 −3 244 34 6 −22 −2 2 42 43 13 −20 −2 2 42 34 15 −18 −2 2 88 90 8 −5 −3 4 522507 21 −3 −3 4 259 276 14 −1 −3 4 158 143 11 1 −3 4 184 159 12 3 −3 4202 201 9 5 −3 4 178 174 8 7 −3 4 301 285 15 9 −3 4 242 240 8 11 −3 4 5256 7 13 −3 4 35 17 10 15 −3 4 104 98 6 −24 −2 4 19 23 18 −22 −2 4 29 3128 −20 −2 4 229 215 8 −18 −2 4 298 273 8 −16 −2 4 175 177 6 −14 −2 4 162172 5 −12 −2 4 210 209 1 −10 −2 4 112 124 10 −8 −2 4 61 56 11 −6 −2 4414 453 21 −4 −2 4 104 120 9 −2 −2 4 260 262 9 0 −2 4 212 196 12 2 −2 4230 219 13 4 −2 4 593 539 30 8 −2 4 107 98 7 10 −2 4 34 42 14 12 −2 4 7265 7 14 −2 4 100 118 6 16 −2 4 0 15 1 18 −2 4 66 63 6 −21 −1 4 69 53 12−19 −1 4 237 210 11 −17 −1 4 125 123 5 −15 −1 4 176 185 5 −13 −1 4 461465 22 −11 −1 4 147 146 11 −9 −1 4 184 192 12 −7 −1 4 287 317 17 −5 −1 4181 185 10 −3 −1 4 676 659 23 −1 −1 4 694 679 25 1 −1 4 454 408 24 3 −14 527 521 18 5 −1 4 226 222 11 7 −1 4 237 240 13 9 −1 4 71 76 5 11 −1 4145 148 6 13 −1 4 236 217 11 15 −1 4 216 184 10 17 −1 4 228 129 8 19 −14 163 147 8 −24 0 4 153 123 10 −22 0 4 157 127 11 −20 0 4 0 17 1 −18 0 4171 162 12 −16 0 4 5 21 5 −14 0 4 0 34 1 −12 0 4 64 55 18 −10 0 4 194179 12 −6 0 4 241 221 13 −4 0 4 145 118 6 −2 0 4 298 297 13 0 0 4 698710 25 2 0 4 358 394 28 4 0 4 318 377 16 6 0 4 324 382 17 8 0 4 130 12710 10 0 4 257 263 7 12 0 4 172 175 6 14 0 4 101 101 8 16 0 4 148 121 918 0 4 196 176 9 20 0 4 47 56 10 −25 1 4 77 78 9 −23 1 4 61 42 14 −21 14 48 53 20 −19 1 4 209 210 14 −17 1 4 129 124 20 −15 1 4 176 134 8 −13 14 428 456 24 −11 1 4 170 146 10 −9 1 4 213 192 11 −7 1 4 323 318 16 −5 14 178 185 7 −3 1 4 650 663 35 1 1 6 486 463 25 3 1 6 491 520 25 5 1 6180 160 10 7 1 6 164 160 10 9 1 6 178 183 13 13 1 6 147 149 10 15 1 6 4243 12 17 1 6 46 16 13 −24 2 6 7 18 7 −22 2 6 61 60 17 −20 2 6 126 108 10−18 2 6 70 64 16 −16 2 6 0 61 1 −4 2 6 529 501 26 −2 2 6 428 366 22 0 26 313 269 16 2 2 6 296 259 16 4 2 6 164 161 12 6 2 6 89 80 14 8 2 6 103120 15 12 2 6 0 23 1 14 2 6 50 52 14 16 2 6 30 36 30 −23 3 6 84 92 11−21 3 6 129 118 10 −19 3 6 57 33 19 3 3 6 131 126 10 5 3 6 253 270 13 73 6 168 180 12 9 3 6 114 114 10 11 3 6 10 51 10 13 3 6 13 26 13 15 3 6 08 1 6 4 6 144 150 11 8 4 6 0 12 1 10 4 6 0 19 1 10 4 6 29 22 28 14 4 6 912 9 −14 −6 7 42 59 10 −12 −6 7 20 7 20 −10 −6 7 58 61 6 −8 −6 7 59 6713 −6 −6 7 83 76 11 −4 −6 7 154 141 7 −2 −6 7 43 47 14 0 −6 7 42 26 14 2−6 7 36 38 19 4 −6 7 45 41 13 −17 −5 7 80 94 5 −15 −5 7 81 85 6 −13 −5 766 70 7 −11 −5 7 180 163 6 −9 −5 7 0 16 1 −7 −5 7 78 80 5 −5 −5 7 44 537 −3 −5 7 52 47 15 −1 −5 7 26 46 26 1 −5 7 73 82 9 3 −5 7 74 97 9 5 −5 771 96 10 7 −5 7 19 35 18 9 −5 7 33 39 32 −22 −4 7 111 104 5 −20 −4 7 2424 23 −18 −4 7 72 84 6 −16 −4 7 67 59 7 −14 −4 7 210 216 11 −12 −4 7 169159 5 −10 −4 7 205 192 4 −8 −4 7 93 96 5 −6 −4 7 185 178 6 −4 −4 7 197189 6 −2 −4 7 190 183 9 0 −4 7 186 191 12 2 −4 7 222 221 17 4 −4 7 174187 11 6 −4 7 106 94 10 8 −4 7 100 101 10 10 −4 7 58 68 15 12 −4 7 37 429 −23 −3 7 50 44 8 −21 −3 7 161 150 6 −19 −3 7 231 222 11 −17 −3 7 194195 6 −15 −3 7 465 447 10 −13 −3 7 210 225 5 −11 −3 7 102 101 3 −16 −2 978 85 6 −14 −2 9 70 72 6 −12 −2 9 158 160 5 −10 −2 9 141 139 4 −8 −2 9143 142 11 −6 −2 9 457 429 24 −4 −2 9 451 452 24 −2 −2 9 210 222 9 0 −29 64 60 5 2 −2 9 162 166 7 4 −2 9 136 145 7 6 −2 9 555 517 21 8 −2 9 215235 9 10 −2 9 134 140 6 12 −2 9 60 61 6 −25 −1 9 118 108 9 −23 −1 9 130122 26 −21 −1 9 191 179 17 −19 −1 9 251 243 9 −17 −1 9 92 87 11 −15 −1 9205 206 6 −13 −1 9 251 270 7 −11 −1 9 423 395 22 −9 −1 9 442 401 24 −7−1 9 322 303 18 −5 −1 9 445 414 21 −3 −1 9 474 459 28 −1 −1 9 85 90 10 1−1 9 347 342 11 3 −1 9 188 196 6 5 −1 9 159 168 8 7 −1 9 91 83 6 9 −1 946 63 10 11 −1 9 63 77 7 13 −1 9 42 44 10 15 −1 9 0 16 1 −26 0 9 3 29 3−24 0 9 0 13 1 −22 0 9 41 69 25 −20 0 9 125 141 10 −18 0 9 54 58 13 −160 9 388 370 13 −14 0 9 308 276 17 −12 0 9 527 542 27 −10 0 9 356 376 19−8 0 9 937 380 48 −6 0 9 348 375 18 −4 0 9 0 21 1 −2 0 9 115 141 9 0 0 9176 201 11 2 0 9 360 363 12 4 0 9 89 84 4 6 0 9 230 235 6 8 0 9 0 13 110 0 9 87 92 5 12 0 9 73 75 7 14 0 9 40 38 12 −27 1 9 45 37 17 −25 1 9118 108 10 −23 1 9 132 121 10 −21 1 9 197 178 12 −19 1 9 259 244 14 −171 9 78 89 13 −15 1 9 193 205 13 −11 1 9 415 395 22 −9 1 9 458 401 23 −71 9 352 303 17 −5 1 9 404 414 23 −3 1 9 550 460 24 −1 1 9 100 90 12 1 19 363 341 12 3 1 9 194 197 6 5 1 9 162 169 6 7 1 9 96 94 6 9 1 9 67 6310 11 1 9 88 77 12 13 1 9 43 43 16 −26 2 9 49 30 16 −24 2 9 56 50 17 −222 9 0 30 1 −20 2 9 227 225 13 −6 2 9 455 429 24 −4 2 9 462 453 24 −2 2 9236 220 12 0 2 9 80 61 9 2 2 9 160 167 6 4 2 9 147 146 5 −21 −3 12 99 935 −19 −3 12 95 112 5 −17 −3 12 53 61 6 −15 −3 12 0 12 1 −13 −3 12 113114 5 −11 −3 12 33 36 12 −9 −3 12 158 150 9 −7 −3 12 190 172 9 −5 −3 1261 51 7 −3 −3 12 153 142 6 −1 −3 12 105 96 5 1 −3 12 148 143 11 −26 −212 64 45 11 −24 −2 12 37 34 14 −22 −2 12 35 41 15 −20 −2 12 57 78 9 −18−2 12 143 182 11 −16 −2 12 225 218 7 −14 −2 12 263 256 8 −12 −2 12 98109 4 −10 −2 12 70 59 5 −8 −2 12 131 135 4 −6 −2 12 238 238 6 −4 −2 12220 243 14 −2 −2 12 140 134 7 0 −2 12 76 71 6 2 −2 12 277 294 11 4 −2 12103 112 7 6 −2 12 202 209 8 8 −2 12 99 87 6 −25 −1 12 50 40 12 −23 −1 12112 98 17 −21 −1 12 138 159 16 −19 −1 12 133 123 15 −17 −1 12 95 101 5−15 −1 12 69 76 8 −13 −1 12 340 351 9 −11 −1 12 178 197 5 −9 −1 12 164172 5 −7 −1 12 191 218 6 −5 −1 12 62 64 6 −3 −1 12 249 240 7 −1 −1 12199 193 6 1 −1 12 151 146 7 3 −1 12 117 105 7 5 −1 12 62 75 7 7 −1 12 7479 7 9 −1 12 51 54 9 11 −1 12 31 35 13 −26 0 12 41 31 28 −24 0 12 127191 10 −22 0 12 62 67 23 −20 0 12 174 152 9 −18 0 12 0 20 1 −16 0 12 138148 6 −14 0 12 12 8 11 −12 0 12 92 108 6 −10 0 12 28 29 27 −8 0 12 176193 7 −6 0 12 280 290 8 −4 0 12 109 115 3 −2 0 12 24 4 20 0 0 12 269 2717 2 0 12 0 14 1 4 0 12 51 61 6 6 0 12 76 70 5 8 0 12 0 23 1 10 0 12 155143 8 12 0 12 36 39 11 −27 1 12 45 41 18 −25 1 12 53 39 18 −23 1 12 9898 11 −21 1 12 122 123 6 −19 1 12 95 100 10 −17 1 12 73 77 12 −15 1 12330 351 17 −11 1 12 184 198 7 −9 1 12 173 171 6 −7 1 12 196 217 6 −5 112 58 65 8 −3 1 12 236 239 7 −1 1 12 182 192 7 1 1 12 142 145 8 3 1 12111 106 9 5 1 12 72 75 7 7 1 12 80 79 8 9 1 12 41 54 16 −18 0 15 0 19 1−16 0 15 75 77 9 −14 0 15 252 244 9 −12 0 15 68 41 8 −10 0 15 52 39 18−8 0 15 278 270 10 −6 0 15 309 278 8 −4 0 15 122 129 4 −2 0 15 99 106 60 0 15 39 36 16 2 0 15 146 144 8 4 0 15 19 10 19 6 0 15 52 43 9 −25 1 1533 33 33 −23 1 15 63 48 13 −21 1 15 110 111 9 −19 1 15 0 16 1 −17 1 15139 149 9 −15 1 15 167 158 16 −13 1 15 122 129 7 −11 1 15 376 357 13 −91 15 261 241 10 −7 1 15 335 315 11 −5 1 15 116 121 6 −3 1 15 187 199 8−1 1 15 53 56 9 1 1 15 183 163 9 3 1 15 47 51 20 −18 2 15 45 56 24 −16 215 185 181 12 −14 2 15 206 189 13 −12 2 15 131 132 10 −10 2 15 121 122 7−8 2 15 124 125 7 −6 2 15 265 273 13 −4 2 15 189 195 18 −2 2 15 177 18811 0 2 15 118 126 14 2 2 15 60 61 7 4 2 15 51 39 8 6 2 15 59 56 9 −13 315 151 155 13 −11 3 15 301 272 15 −9 3 15 133 116 9 −7 3 15 131 127 9 −53 15 71 78 8 −3 3 15 36 28 17 −1 3 15 70 79 15 1 3 15 105 96 6 3 3 15 2716 21 −8 4 15 140 143 9 −6 4 15 94 92 9 −4 4 15 54 42 13 −2 4 15 0 6 1 04 15 53 48 9 −11 −5 16 100 98 7 −18 −4 16 103 94 9 −16 −4 16 77 66 6 −14−4 16 196 164 7 −12 −4 16 64 61 7 −10 −4 16 32 27 14 −8 −4 16 19 25 19−6 −4 16 16 22 16 −4 −4 16 17 30 17 −2 −4 16 38 59 21 −23 −3 16 41 36 12−21 −3 16 21 17 21 −19 −3 16 0 16 1 −17 −3 16 39 48 10 −15 −3 16 40 5113 −13 −3 16 173 174 16 −11 −3 16 48 41 10 −9 −3 16 65 68 7 −7 −3 16 7283 6 −5 −3 16 116 117 5 −24 −2 16 47 44 9 −22 −2 16 29 46 28 −20 −2 1631 36 20 −18 −2 16 85 95 8 −16 −2 16 206 188 8 −14 −2 16 202 188 6 −12−2 16 221 194 6 −10 −2 16 347 339 10 −8 −2 16 77 78 7 −6 −2 16 88 98 7−4 −2 16 15 20 14 −2 −2 16 56 63 8 −16 0 19 22 24 22 −14 0 19 12 10 11−12 0 19 58 68 9 −10 0 19 16 39 15 −8 0 19 143 138 6 −6 0 19 69 61 9 −40 19 19 24 19 −2 0 19 38 37 13 0 0 19 94 76 6 −23 1 19 133 114 9 −21 119 45 38 19 −19 1 19 118 122 8 −17 1 19 92 104 14 −15 1 19 38 27 16 −131 19 31 58 27 −11 1 19 48 68 12 −9 1 19 114 118 9 −7 1 19 0 23 1 −5 1 1963 57 8 −3 1 19 33 35 33 −22 2 19 56 37 13 −20 2 19 36 49 36 −18 2 19 7864 11 −16 2 19 31 48 31 −14 2 19 40 44 19 −12 2 19 0 20 1 −10 2 19 62 639 −8 2 19 60 61 9 −6 2 19 39 52 14 −4 2 19 85 76 10 −2 2 19 67 64 10 −173 19 79 84 10 −15 3 19 51 45 17 −13 3 19 0 24 1 −11 3 19 25 27 24 −9 319 113 105 6 −7 3 19 75 66 7 −5 3 19 53 53 8 −15 −3 20 30 17 30 −13 −320 92 84 6 −11 −3 20 0 5 1 −9 −3 20 31 30 11 −20 −2 20 59 60 7 −18 −2 2016 43 16 −16 −2 20 59 39 9 −14 −2 20 59 54 10 −12 −2 20 0 8 1 −10 −2 2062 49 9 −8 −2 20 59 55 8 −6 −2 20 22 16 22 −23 −1 20 10 29 9 −21 −1 2066 47 7 −19 −1 20 47 27 20 −17 −1 20 0 14 1 −15 −1 20 80 78 6 −13 −1 2047 56 9 −11 −1 20 62 70 10 −9 −1 20 91 89 7 −7 −1 20 119 108 7 −5 −1 2053 34 9 −3 −1 20 74 74 6 −22 0 20 34 27 17 −20 0 20 143 124 7 −18 0 2027 39 26 −16 0 20 48 46 11 −14 0 20 29 31 28 −12 0 20 171 156 8 −10 0 20171 143 7 −16 −2 2 0 32 1 −14 −2 2 233 232 6 −12 −2 2 417 450 9 −10 −2 2873 787 45 −8 −2 2 97 113 9 −6 −2 2 690 741 38 −4 −2 2 151 161 12 −2 −22 184 215 12 0 −2 2 494 462 14 2 −2 2 488 531 30 10 −2 2 137 128 5 12 −22 218 213 10 14 −2 2 83 96 7 16 −2 2 87 108 7 18 −2 2 155 147 8 20 −2 231 49 15 −23 −1 2 79 62 7 −21 −1 2 28 35 27 −19 −1 2 111 113 6 −17 −1 269 63 9 −15 −1 2 121 117 5 −13 −1 2 172 172 7 −11 −1 2 375 405 22 −9 −12 203 198 12 −7 −1 2 933 965 48 −5 −1 2 697 678 25 −3 −1 2 422 411 14 −1−1 2 666 618 23 3 −1 2 44 56 5 5 −1 2 373 413 20 7 −1 2 173 197 10 9 −12 328 317 17 11 −1 2 235 244 6 13 −1 2 155 154 6 15 −1 2 110 111 7 17 −12 107 94 8 19 −1 2 50 56 11 21 −1 2 114 100 7 −22 0 2 36 38 35 −20 0 278 80 11 −18 0 2 92 105 11 −16 0 2 0 4 1 −14 0 2 152 146 8 −12 0 2 118127 11 −10 0 2 434 460 22 −8 0 2 831 815 42 −6 0 2 32 40 32 −4 0 2 909875 46 −2 0 2 99 107 4 0 0 2 265 250 7 2 0 2 354 339 18 4 0 2 437 497 226 0 2 116 136 3 8 0 2 196 274 11 10 0 2 57 52 15 12 0 2 134 145 5 14 0 278 74 7 16 0 2 43 63 13 18 0 2 38 41 22 −23 1 2 44 62 14 −21 1 2 50 3516 −19 1 2 95 113 11 −17 1 2 64 63 17 −15 1 2 122 116 9 −13 1 2 167 1717 −11 1 2 417 405 20 −9 1 2 224 198 11 −7 1 2 941 964 48 −5 1 2 713 68025 −3 1 2 401 410 15 −1 1 2 628 621 35 1 1 2 1352 1283 69 3 1 2 45 52 135 1 2 392 413 19 7 1 2 183 195 10 9 1 2 333 319 17 11 1 2 239 244 9 13 12 155 153 8 15 1 2 89 111 10 17 1 2 94 93 10 −22 2 2 44 43 23 −20 2 2 2733 27 −18 2 2 57 90 20 −16 2 2 0 32 1 −14 2 2 237 232 13 −12 2 2 394 42821 −8 2 2 129 115 9 −1 1 4 720 680 35 1 1 4 467 409 23 3 1 4 480 520 285 1 4 218 222 13 7 1 4 239 241 13 9 1 4 74 76 8 11 1 4 148 148 7 13 1 4236 216 12 15 1 4 181 146 6 −24 2 4 30 23 29 −22 2 4 0 31 1 −20 2 4 229215 13 −18 2 4 299 273 15 −16 2 4 167 178 11 −14 2 4 153 171 10 −4 2 4130 119 8 −2 2 4 263 261 14 0 2 4 213 193 12 2 2 4 231 220 13 4 2 4 587541 30 6 2 4 310 288 17 8 2 4 116 99 6 10 2 4 50 42 15 12 2 4 88 85 1118 2 4 66 64 11 −23 3 4 30 34 29 −21 3 4 44 59 29 −19 3 4 41 22 41 −17 34 153 169 11 15 3 4 86 97 12 17 3 4 46 52 19 10 4 4 84 95 11 12 4 4 2230 21 14 4 4 34 14 34 16 4 4 31 11 31 −14 −6 5 11 27 10 −12 −6 5 74 7511 −10 −6 5 30 18 13 −8 −6 5 105 99 5 −6 −6 5 38 36 9 −4 −6 5 134 160 7−2 −6 5 117 110 4 0 −6 5 32 27 22 2 −6 5 71 59 9 4 −6 5 92 84 8 6 −6 564 54 9 −17 −6 5 14 8 13 −15 −5 5 0 25 1 −13 −5 5 66 67 7 −11 −5 5 160156 5 −9 −5 5 266 255 8 −7 −5 5 279 256 8 −5 −5 5 190 189 5 −3 −5 5 123125 5 −1 −5 5 77 78 5 1 −5 5 166 163 10 3 −5 5 61 64 11 5 −5 5 30 40 307 −5 5 92 97 9 9 −5 5 60 45 13 11 −5 5 24 28 23 −20 −4 5 28 13 20 −18 −45 20 21 20 −16 −4 5 54 65 9 −14 −4 5 218 247 6 −12 −4 5 182 10 6 −10 −45 219 206 6 −8 −4 5 113 103 3 −6 −4 5 127 113 5 −4 −4 5 178 181 5 −2 −45 116 107 4 0 −4 5 125 102 5 2 −4 5 112 103 19 4 −4 5 57 66 12 6 −4 5157 157 11 8 −4 5 71 80 12 10 −4 5 43 47 24 12 −4 5 54 42 17 14 −4 5 2924 23 −23 −3 5 51 50 7 −21 −3 5 57 65 8 −19 −3 5 190 191 8 −17 −3 5 206193 6 −15 −3 5 38 39 11 −13 −3 5 196 206 6 −11 −3 5 118 119 4 −9 −3 5246 250 5 −9 −3 7 313 303 6 −7 −3 7 92 80 3 −5 −3 7 255 251 7 −3 −3 7201 201 8 −1 −3 7 141 143 7 1 −3 7 177 166 8 3 −3 7 225 233 12 5 −3 7149 132 9 7 −3 7 233 226 13 9 −3 7 69 58 14 −24 −2 7 30 33 29 −22 −2 770 48 12 −20 −2 7 143 127 7 −18 −2 7 65 57 10 −16 −2 7 180 182 6 −14 −27 154 167 5 −12 −2 7 140 141 4 −10 −2 7 266 246 15 −8 −2 7 152 150 10 −6−2 7 242 252 15 −4 −2 7 225 294 13 −2 −2 7 208 193 12 0 −2 7 160 160 124 −2 7 80 83 5 6 −2 7 204 207 8 8 −2 7 0 15 1 10 −2 7 193 210 8 12 −2 760 74 6 14 −2 7 130 119 7 16 −2 7 55 58 5 −25 −1 7 73 65 9 −23 −1 7 3582 35 −21 −1 7 104 108 14 −19 −1 7 258 252 10 −17 −1 7 154 157 6 −15 −17 388 397 11 −13 −1 7 157 152 10 −11 −1 7 360 291 19 −9 −1 7 814 760 43−7 −1 7 783 724 40 −5 −1 7 915 845 48 −3 −1 7 102 115 7 −1 −1 7 218 2078 1 −1 7 0 28 1 3 −1 7 500 522 29 5 −1 7 475 492 13 7 −1 7 285 276 9 9−1 7 142 142 8 11 −1 7 271 269 13 13 −1 7 36 21 14 15 −1 7 55 51 8 17 −17 0 31 1 −26 0 7 29 41 29 −24 0 7 0 5 1 −22 0 7 63 72 13 −20 0 7 45 5222 −18 0 7 98 94 11 −16 0 7 55 82 14 −14 0 7 159 160 12 −12 0 7 274 22815 −10 0 7 312 305 17 −8 0 7 176 158 7 −6 0 7 263 307 15 −4 0 7 750 80334 −2 0 7 750 790 27 0 0 7 805 867 41 2 0 7 451 519 23 4 0 7 88 81 11 60 7 156 153 5 8 0 7 193 174 6 10 0 7 360 348 9 12 0 7 70 65 6 14 0 7 018 1 16 0 7 9 45 8 −25 1 7 59 66 15 −23 1 7 63 62 14 −21 1 7 114 108 10−19 1 7 277 253 13 −17 1 7 154 156 10 −15 1 7 375 397 19 −9 1 7 831 76042 −7 1 7 788 722 40 −5 1 7 944 844 47 −3 1 7 119 116 9 −1 1 7 223 20712 1 1 7 0 26 1 3 1 7 566 522 26 6 2 9 521 517 18 8 2 9 220 236 13 10 29 126 140 6 12 2 9 62 60 18 14 2 9 0 23 1 −3 3 9 98 113 10 −1 3 9 357362 19 1 3 9 308 293 15 3 3 9 368 363 18 5 3 9 211 206 8 7 3 9 82 79 7 93 9 59 64 17 11 3 9 69 50 8 13 3 9 76 69 6 2 4 9 139 142 10 4 4 9 94 9510 6 4 9 0 20 1 8 4 9 92 73 9 10 4 9 64 55 8 7 5 9 31 29 30 −8 −6 10 128126 6 −6 −6 10 24 22 24 −4 −6 10 56 57 10 −2 −6 10 34 50 20 0 −6 10 0 131 −17 −5 10 0 37 1 −15 −5 10 59 72 9 −13 −5 10 37 46 36 −11 −5 10 52 459 −9 −5 10 90 83 6 −7 −5 10 80 68 9 −5 −5 10 51 59 30 −3 −5 10 0 25 1 −1−5 10 115 137 8 1 −5 10 157 159 10 3 −5 10 126 132 9 5 −5 10 86 101 8−22 −4 10 46 43 10 −20 −4 10 71 63 7 −18 −4 10 93 97 6 −16 −4 10 83 79 6−14 −4 10 110 111 4 −12 −4 10 198 196 6 −10 −4 10 133 130 13 −8 −4 10 1720 17 −6 −4 10 68 71 6 −4 −4 10 51 37 11 −2 −4 10 306 330 15 0 −4 10 134141 9 2 −4 10 175 172 11 4 −4 10 52 45 16 6 −4 10 18 44 18 8 −4 10 68 7711 −23 −3 10 139 120 13 −21 −3 10 102 93 10 −19 −3 10 191 189 9 −17 −310 52 54 9 −15 −3 10 262 295 8 −13 −3 10 268 257 6 −11 −3 10 30 34 10 −9−3 10 85 77 9 −7 −3 10 132 145 5 −5 −3 10 182 173 8 −3 −3 10 165 162 7−1 −3 10 105 96 11 1 −3 10 257 238 13 3 −3 10 369 376 18 −26 −2 10 73 6811 −24 −2 10 75 56 7 −22 −2 10 53 44 9 −20 −2 10 20 22 19 −18 −2 10 3537 16 −16 −2 10 41 61 13 −14 −2 10 162 157 6 −12 −2 10 256 247 6 −10 −210 116 102 8 −8 −2 10 299 288 7 −6 −2 10 256 249 7 −4 −2 10 143 144 7 −2−2 10 92 81 6 0 −2 10 164 172 8 2 −2 10 152 157 7 4 −2 10 108 110 7 6 −210 59 61 6 8 −2 10 28 34 16 10 −2 10 116 104 6 12 −2 10 23 26 16 −14 212 42 34 25 −12 2 12 91 108 10 −10 2 12 67 58 12 −8 2 12 119 135 9 −6 212 243 238 13 −4 2 12 230 244 10 −2 2 12 138 135 12 0 2 12 73 71 8 2 212 273 294 20 4 2 12 109 112 10 6 2 12 195 209 8 8 2 12 89 86 6 10 2 1263 58 6 −9 3 12 142 150 11 −7 3 12 163 172 13 −5 3 12 57 51 16 −3 3 12149 142 12 −1 3 12 112 98 9 1 3 12 130 143 7 3 3 12 75 74 9 5 3 12 120126 11 7 3 12 79 70 7 9 3 12 65 66 6 −4 4 12 76 66 11 −2 4 12 63 58 13 04 12 94 89 10 2 4 12 85 83 9 4 4 12 60 48 11 6 4 12 38 29 18 −17 −5 1360 55 10 −15 −5 13 134 118 12 −13 −5 13 102 78 11 −11 −5 13 87 68 6 −9−5 13 112 94 5 −7 −5 13 132 117 10 −5 −5 13 80 78 9 −3 −5 13 57 52 11 −1−5 13 58 56 10 1 −5 13 56 61 10 −20 −4 13 94 82 11 −18 −4 13 27 50 27−16 −4 13 43 44 12 −14 −4 13 172 160 20 −12 −4 13 125 134 6 −10 −4 13196 222 12 −8 −4 13 114 130 6 −6 −4 13 108 116 5 −4 −4 13 39 41 27 −2 −413 56 55 14 0 −4 13 82 85 10 2 −4 13 80 70 10 −23 −3 13 55 39 7 −21 −313 148 131 6 −19 −3 13 118 134 6 −17 −3 13 52 59 8 −15 −3 13 43 59 9 −13−3 13 60 73 9 −11 −3 13 117 110 7 −9 −3 13 80 81 7 −7 −3 13 296 280 21−5 −3 13 178 199 24 −3 −3 13 158 160 10 −26 −2 13 93 70 6 −24 −2 13 3835 13 −22 −2 13 42 52 10 −20 −2 13 121 137 5 −18 −2 13 111 137 5 −16 −213 190 178 7 −14 −2 13 87 87 6 −12 −2 13 310 283 7 −10 −2 13 154 143 4−8 −2 13 119 124 5 −6 −2 13 240 232 8 −4 −2 13 117 122 7 −2 −2 13 197186 9 0 −2 13 79 84 6 2 −2 13 41 54 9 4 −2 13 36 46 11 6 −2 13 153 146 7−27 −1 13 43 55 17 −25 −1 13 92 82 7 −23 −1 13 95 89 8 −21 −1 13 83 91 6−19 −1 13 126 124 6 −17 −1 13 257 248 7 −15 −1 13 181 190 6 −13 −1 13 3940 24 0 −2 16 0 15 1 2 −2 16 83 67 6 −25 −1 16 101 85 5 −23 −1 16 63 527 −21 −1 16 80 75 8 −19 −1 16 50 48 9 −17 −1 16 135 152 5 −15 −1 16 314331 9 −13 −1 16 258 272 13 −11 −1 16 243 237 11 −9 −1 16 312 151 8 −7 −116 174 213 6 −5 −1 16 219 16 7 −3 −1 16 29 16 28 −1 −1 16 161 153 8 1 −116 65 68 8 3 −1 16 57 55 8 5 −1 16 52 40 7 −26 0 16 70 48 7 −24 0 16 347 25 −22 0 16 112 109 14 −20 0 16 51 60 9 −18 0 16 160 183 11 −16 0 1681 100 9 −14 0 16 534 561 34 −12 0 16 98 86 6 −10 0 16 363 337 12 −8 016 102 102 12 −6 0 16 144 149 7 −4 0 16 12 21 11 −2 0 16 123 132 7 0 016 9 35 8 2 0 16 96 93 7 4 0 16 94 78 6 6 0 16 26 14 25 −23 1 16 74 5111 −21 1 16 95 75 10 −19 1 16 36 49 36 −17 1 16 151 153 11 −15 1 16 322236 11 −13 1 16 262 270 12 −11 1 16 225 236 14 −9 1 16 309 299 16 −7 116 164 152 13 −5 1 16 176 212 9 −3 1 16 20 14 19 −1 1 16 159 153 18 1 116 77 68 6 3 1 16 58 56 11 5 1 16 26 40 23 −20 2 16 13 36 13 −18 2 16 8094 11 −16 2 16 208 189 12 −14 2 16 192 190 13 −12 2 16 221 193 13 −10 216 339 338 17 −8 2 16 81 79 8 −6 2 16 94 98 17 −4 2 16 10 21 10 −2 2 1648 63 9 0 2 16 28 15 28 2 2 16 88 67 5 4 2 16 0 23 1 −15 3 16 0 51 1 −133 16 187 174 11 −11 3 16 67 40 15 −9 3 16 63 69 14 −7 3 16 63 83 12 −5 316 109 118 6 −3 3 16 88 99 6 −1 3 16 77 77 7 1 3 16 60 53 7 −8 4 16 0 251 −6 4 16 0 22 1 −4 4 16 28 29 27 −2 4 16 61 60 9 −18 −4 16 20 32 19 −16−4 17 64 67 6 −14 −4 17 62 61 7 −12 −4 17 156 141 6 −10 −4 17 43 48 8 −8−4 17 59 52 13 −6 −4 17 50 52 14 −21 −3 17 0 15 1 −19 −3 17 51 60 10 −17−3 17 75 74 7 −15 −3 17 84 83 6 −8 0 20 14 22 13 −6 0 20 49 29 11 −4 020 62 45 8 −23 1 20 50 29 14 −21 1 20 42 46 21 −19 1 20 34 27 21 −17 120 0 14 1 −15 1 20 65 78 8 −13 1 20 55 56 10 −11 1 20 82 70 11 −9 1 2091 88 6 −7 1 20 116 109 6 −5 1 20 32 34 32 −20 2 20 72 60 9 −18 2 20 043 1 −16 2 20 0 39 1 −14 2 20 66 53 9 −12 2 20 0 7 1 −10 2 20 55 48 10−8 2 20 41 56 13 −6 2 20 0 15 1 −15 3 20 12 16 11 −13 3 20 82 85 9 −11 320 0 6 1 −9 3 20 0 29 1 −16 −2 21 44 38 12 −14 −2 21 53 19 9 −12 −2 2148 25 11 −10 −2 21 17 4 17 −8 −2 21 26 23 26 −21 −1 21 35 32 20 −19 −121 38 45 20 −17 −1 21 79 59 9 −15 −1 21 91 75 7 −13 −1 21 44 53 14 −11−1 21 64 71 9 −9 −1 21 43 31 12 −7 −1 21 40 35 12 −22 0 21 26 4 25 −20 021 26 10 25 −18 0 21 0 1 1 −16 0 21 91 72 6 −14 0 21 41 46 12 −12 0 21104 87 6 −8 0 21 20 16 20 −6 0 21 36 9 14 −21 1 21 44 33 16 −19 1 21 3646 20 −17 1 21 67 59 7 −15 1 21 78 75 6 −13 1 21 50 54 10 −11 1 21 68 717 −9 1 21 44 30 10 −7 1 21 27 35 27 −18 2 21 27 32 26 −16 2 21 36 37 18−14 2 21 0 18 1 −12 2 21 23 25 23 −10 2 21 0 4 1 −8 2 21 6 23 6 −18 0 2216 31 16 −16 0 22 40 40 40 −14 0 22 29 7 28 −17 1 22 33 31 14 −15 1 2268 34 10 −13 1 22 86 76 6 −11 1 22 68 71 8

REFERENCES

-   1. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.28 cycle2    beta (release 25-10-2005 CrysAlis171.NET) (compiled Oct. 25 2005,    08:50:05). Empirical absorption correction using spherical    harmonics, implemented in SCALE3 ABSPACK scaling algorithm.-   2. CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.28 cycle2    beta; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.28 cycle2    beta.-   3. G. M. Sheidrick, Acta Crystallogr. 1990, A46, 467-473.-   4. G. M. Sheldrick, SHELXL93. Program for the Reminement of Crystal    Structures, Univ. of Götttingen, Germany.-   5. International Tables for Crystallography, Ed. A. J. C. Wilson,    Kluwer:Dordrecth, 1992, Vol. C.

Example 2 Synthesis of 24F2-DM

The preparation of 24F2-DM having the basic structure I can beaccomplished by a common general method otherwise referred to as thecondensation of a bicyclic Windaus-Grundmann type ketone II with theallylic phosphine oxide III to the corresponding 19-nor-vitamin D analogIV followed by deprotection at C-1 and C-3 in the latter compound IV toobtain compound I (24F2-DM).

In phosphine oxide III, Y₁ and Y₂ are preferably hydroxy-protectinggroups such as silyl protecting groups. The t-butyldimethylsilyl (TMDMS)group is an example of a particularly useful hydroxy-protecting group.The process described above represents an application of the convergentsynthesis concept, which has been applied effectively to the preparationof numerous vitamin D compounds (see Lythgoe et al., J. Chem. Soc.Perkin Trans. 1, 590 (1978); Lythgoe, Chem. Soc. Rev. 9, 449 (1983); Tohet al., J. Org. Chem. 48, 1414 (1983); Baggiolini et al., J. Org. Chem.51, 3098 (1986); Sardina et al., J. Org. Chem. 51, 1264 (1986); J. Org.Chem. 51, 1269 (1986); DeLuca et al., U.S. Pat. No. 5,086,191; DeLuca etal., U.S. Pat. No. 5,536,713; and DeLuca et al., U.S. Pat. No. 5,843,928all of which are hereby incorporated by reference in their entirety andfor all purposes as if fully set forth herein.

Phosphine oxide III is a convenient reagent that can be used to preparea large number of 19-nor-vitamin D compounds and is prepared accordingto the procedures described by Sicinski et al., J. Med. Chem., 41, 4662(1998), DeLuca et al., U.S. Pat. No. 5,843,928; Perlman et al.,Tetrahedron Lett. 32, 7663 (1991); and DeLuca et al., U.S. Pat. No.5,086,191 which are hereby incorporated by reference in their entiretyas if fully set forth herein.

An overall process for the synthesis of compound I is illustrated anddescribed more completely in U.S. Pat. No. 5,843,928 entitled“2-Alkylidene-19-Nor-Vitamin D Compounds,” the specification of which isspecifically incorporated herein by reference.

We claim:
 1. A compound having the formula

in crystalline form, and named(20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃.
 2. A crystallineform of (20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃ havingmolecular packing arrangement defined by space group C2 and unit celldimensions a=23.88 Å b=6.16 Å c=19.63 Å α=90°, β=121.83° and γ=90°.
 3. Athree dimensional structure for(20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃ as defined by themolecular packing arrangement set forth in claim
 2. 4. A method ofpurifying (20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃, comprisingthe steps of: (a) preparing a solvent comprising hexane; (b) adding aproduct containing (20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃ tobe purified to said hexane to form a suspension of the product in thehexane; (c) adding 2-propanol dropwise to the suspension to form amixture of the product in the hexane and 2-propanol; (d) heating themixture to dissolve the product containing(20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃ to be purified insaid mixture; (e) cooling said mixture and dissolved product belowambient temperature for a sufficient amount of time to form aprecipitate of (20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃crystals; and (f) separating the(20R)-19-nor-24-difluoro-1α,25-dihydroxyvitamin D₃ crystals from thesolvent.
 5. The method of claim 4 including the further step of allowingsaid solvent and dissolved product to cool to ambient temperature priorto cooling below ambient temperature.
 6. The method of claim 4 whereinthe step of separating comprises filtering the mixture and precipitateto obtain the crystals.
 7. The method of claim 4 including a furtherstep (g) comprising repeating steps (a) through (f) using the recoveredcrystals from step (f) as the product of step (b).
 8. The method ofclaim 4 wherein said mixture comprises about 15% 2-propanol and about85% hexane by volume.